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CN103222092A - Non-aqueous electrolyte secondary battery - Google Patents

Non-aqueous electrolyte secondary battery Download PDF

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Publication number
CN103222092A
CN103222092A CN2011800539492A CN201180053949A CN103222092A CN 103222092 A CN103222092 A CN 103222092A CN 2011800539492 A CN2011800539492 A CN 2011800539492A CN 201180053949 A CN201180053949 A CN 201180053949A CN 103222092 A CN103222092 A CN 103222092A
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size particles
nano size
particle
mutually
negative pole
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CN103222092B (en
Inventor
西久保英郎
西村健
谷俊夫
幡谷耕二
岛田道宏
久保田昌明
阿部英俊
江黑高志
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FUKUKAWA DENSHI Co Ltd
Furukawa Electric Co Ltd
Furukawa Battery Co Ltd
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FUKUKAWA DENSHI Co Ltd
Furukawa Electric Co Ltd
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Publication of CN103222092A publication Critical patent/CN103222092A/en
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0567—Liquid materials characterised by the additives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386—Silicon or alloys based on silicon
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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  • Condensed Matter Physics & Semiconductors (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Nanotechnology (AREA)
  • Inorganic Chemistry (AREA)
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  • Battery Electrode And Active Subsutance (AREA)
  • Secondary Cells (AREA)

Abstract

The present invention addresses the problem of providing a non-aqueous electrolyte secondary battery which can have high capacity and good cycle properties. The solution is a non-aqueous electrolyte secondary battery characterized in that a negative electrode active material for a negative electrode comprises nano-sized particles each of which contains element X and element M and has at least a first phase that comprises element Si or a solid solution of Si and a second phase that comprises a compound composed of Si and element M, and is also characterized in that an electrolytic solution contains an organic material that has an unsaturated bond in the molecule and can be reduction-polymerized, wherein the element X is at least one element selected from the group consisting of Si, Sn, Al, Pb, Sb, Bi, Ge, In and Zn and the element M is at least one element selected from the group consisting of transition metal elements belong to Groups 4-11.

Description

Rechargeable nonaqueous electrolytic battery
Technical field
The present invention relates to a kind of rechargeable nonaqueous electrolytic battery, particularly relate to the rechargeable nonaqueous electrolytic battery of a kind of high power capacity and cycle characteristics excellence.
Background technology
Lithium rechargeable battery mainly is used in portable machine, is accompanied by the miniaturization of using machine and multifunction and is required high capacity.Yet the theoretical capacity of carbon-based materials such as the Delanium of the negative electrode active material of present employed lithium rechargeable battery or native graphite is 372mAh/g, can not increase to more than it by the expectation capacity.
Therefore, the bigger silicon (Si) of theoretical capacity and the negative pole (for example with reference to patent documentation 1) of tin metal materials such as (Sn) or its oxide material have been proposed to use, though it has been subjected to gazing at, though but these materials several circulation degree in the early stage shows very high capacity, but shrink the micronizing that causes because of the expansion of active material by repeating to discharge and recharge generation, and negative electrode active material comes off from collector body, therefore has the problem of the non-constant of cycle characteristics.
So, following method has been proposed: by utilize mechanochemical reaction mixing Si or Sn etc. can embed Li composition, and can not embed compositions such as the Cu of Li or Fe, thereby suppress the deterioration (for example with reference to patent documentation 2) that causes because of charge and discharge cycles.
On the other hand, as the method for making of electrode, following method has been proposed: utilize CVD method, sputtering method, vapour deposition method or galvanoplastic that the film of these materials is formed at (for example patent documentation 3) on the collector body.And then, as making the stable method of overlay film of utilizing the electrode surface that this method forms, proposed in electrolyte, to add the method (for example patent documentation 4) of cyclic carbonate with unsaturated bond.
The prior art document
Patent documentation
Patent documentation 1: Japanese kokai publication hei 07-29602 communique
Patent documentation 2: TOHKEMY 2005-78999 communique
Patent documentation 3: Japanese kokai publication hei 11-135115 communique
Patent documentation 4: TOHKEMY 2004-171877 communique
Summary of the invention
Invent problem to be solved
Yet, the invention of record is difficult to evenly disperse each composition with the nano-scale grade in the patent documentation 2, particularly the change in volume of the silicon that is practical as the expectation of negative material when discharging and recharging is big, and breaks easily, can't fully prevent the deterioration of cycle characteristics.
In addition, though the invention of record forms negative electrode active material layer by utilizing CVD method, sputtering method, vapour deposition method or galvanoplastic in patent documentation 3 and the patent documentation 4, the deterioration that can to a certain degree suppress cycle characteristics, but the thickness of negative electrode active material layer only can form thin membrane electrode, because of active material quantity not sufficient when constituting lithium secondary battery is difficult to practicability.And then, though the invention of record forms the decomposition that firm epithelium suppresses electrolyte by the surface at the active material layer of membrane electrode in the patent documentation 4, the deterioration that can suppress cycle characteristics, the effect but the application type electrode in the past that employing utilizes rubbing method to form active material layer can't be inhibited.
The present invention finishes in view of the above problems, and its purpose has been high power capacity accomplished and the rechargeable nonaqueous electrolytic battery of good cycle characteristics.
Be used to solve the means of problem
The present application people furthers investigate in order to reach above-mentioned purpose, found that, by using the negative electrode active material of the nano-scale grade that mainly has the lithium embeddability, can suppress the micronizing of negative electrode active material.And then find, by embed lithium the 1st with the 2nd engaging of not embedding lithium by the interface, can suppress because of discharging and recharging the volumetric expansion of the 1st phase that causes.Find in addition, forming on the electrode under the situation of negative electrode active material layer with rubbing method at the negative electrode active material that uses this kind nano-scale, by electrolyte is comprised have unsaturated bond can reductive polymerization organic substance, thereby form stable epithelium on the surface of negative electrode active material layer, suppress the decomposition of electrolyte.Finally find that then the electrical arrangement of the material that negative pole comprises is depended in the formation of this kind epithelium, and can demonstrate the form of more effective and diversified negative electrode active material.The present invention is based on these discoveries and finish.
That is, the invention provides following invention.
(1) a kind of rechargeable nonaqueous electrolytic battery, it is characterized in that, it has and can embed and the positive pole of removal lithium embedded ion, can embed and the negative pole of removal lithium embedded ion, and be disposed at dividing plate between described positive pole and the described negative pole, and, with described positive pole, described negative pole and described dividing plate are arranged in the nonaqueous electrolytic solution with lithium-ion-conducting, wherein, the negative electrode active material of described negative pole comprises the 1st particle that contains element X, and contain the 2nd particle of element M, described element X is selected from by Si, Sn, Al, Pb, Sb, Bi, Ge, In, at least a kind of element in the group that Zn forms, described element M is the a kind of element that is selected from the group of being made up of the transition metal of the 4th～11 family, described the 1st particle is made of monomer or the solid solution of described element X, described the 2nd particle is made of the monomer or the compound of described element M, and described electrolyte contains and has unsaturated bond in the molecule, and organic substance that can reductive polymerization.
(2) according to (1) described rechargeable nonaqueous electrolytic battery, wherein, the average grain diameter of described the 1st particle is 2nm～500nm, and the average grain diameter of described the 2nd particle is 2nm～10 μ m.
(3) according to (1) described rechargeable nonaqueous electrolytic battery, wherein, in the described negative pole, the surface of described the 2nd particle of the surface lies of described the 1st particle is in 1 μ m.
(4) a kind of non-hydrolysis electrolyte secondary battery, it is characterized in that, it has and can embed and the positive pole of removal lithium embedded ion, can embed and the negative pole of removal lithium embedded ion, and be disposed at dividing plate between described positive pole and the described negative pole, and, with described positive pole, described negative pole and described dividing plate are arranged in the nonaqueous electrolytic solution with lithium-ion-conducting, wherein, the negative electrode active material of described negative pole is made of the nano size particles of containing element X and element M, described element X is selected from by Si, Sn, Al, Pb, Sb, Bi, Ge, In, 1 kind of element in the group that Zn forms, described element M is at least a kind of element that is selected from the group of being made up of the transition metal of the 4th～11 family, described nano size particles has the 1st phase as the monomer of described element X or solid solution at least, reach the 2nd phase as the monomer or the compound of described element M, and described electrolyte contains and has unsaturated bond in the molecule, and organic substance that can reductive polymerization.
(5) according to (4) described non-hydrolysis electrolyte secondary battery, wherein, described nano size particles the described the 1st with the described the 2nd the two is exposed to outer surface mutually, and by interface, the outer surface of described the 1st phase is dome shape roughly.
(6) according to (4) described non-hydrolysis electrolyte secondary battery, wherein, the average grain diameter of described nano size particles is 2nm～500nm.
(7) according to (4) described non-hydrolysis electrolyte secondary battery, wherein, the further containing element M[' of described nano size particles, it is at least a kind of element that is selected from the group of being made up of Cu, Fe, Co, Ni, Ca, Sc, Ti, V, Cr, Mn, Sr, Y, Zr, Nb, Mo, Tc, Ru, Rh, Ba, lanthanide series (except Ce and Pm), Hf, Ta, W, Re, Os, Ir, described element M ' be and constitute the described the 2nd mutually the diverse element of described element M; And further have as described element M ' monomer or another the 2nd phase of compound.
(8) according to (4) described non-hydrolysis electrolyte secondary battery, wherein, the further containing element X ' of described nano size particles, it is at least a kind of element that is selected from the group of being made up of Si, Sn, Al, Pb, Sb, Bi, Ge, In, Zn, and further has the 3rd phase as monomer or the solid solution of described element X '.
(9) according to (8) described non-hydrolysis electrolyte secondary battery, wherein, the described the 3rd reaches the described the 2nd at least one joint in mutually mutually by interface and the described the 1st.
(10) according to (1) described non-hydrolysis electrolyte secondary battery, wherein, described the 1st particle is (4) described nano size particles.
(11) according to (1) or (4) described non-hydrolysis electrolyte secondary battery, wherein, having unsaturated bond and organic substance that can reductive polymerization in the described molecule is at least a kind that is selected from the group of being made up of fluorinated ethylene carbonate, vinylene carbonate and derivative thereof and vinylethylene carbonate.
(12)) according to (11) described non-hydrolysis electrolyte secondary battery, wherein, having unsaturated bond and organic addition that can reductive polymerization in the described molecule is the 0.1 weight %～10 weight % of electrolyte weight.
(13) according to (1) or (4) described non-hydrolysis electrolyte secondary battery, wherein, described negative pole is coated collector body and dry formation by the coating fluid that will comprise negative electrode active material, electric conducting material and binding material at least.
The invention effect
According to the present invention, can be accomplished the rechargeable nonaqueous electrolytic battery of high power capacity and good cycle characteristics.
Description of drawings
Fig. 1 is the schematic cross-section of an example of demonstration rechargeable nonaqueous electrolytic battery of the present invention.
Fig. 2 is the schematic diagram of an example of the formation of the negative electrode active material of demonstration the 1st execution mode.
(a)～(c) of Fig. 3 is the summary sectional view of the nano size particles of the 2nd execution mode.
The (a) and (b) of Fig. 4 are the summary sectional view of the nano size particles of the 2nd execution mode.
The (a) and (b) of Fig. 5 are the summary sectional view of the nano size particles of the 2nd execution mode.
(a)～(c) of Fig. 6 is the summary sectional view of the nano size particles of the 3rd execution mode.
(a)～(b) of Fig. 7 is the summary sectional view of the nano size particles of the 3rd execution mode.
Fig. 8 is the figure of the manufacturing installation of demonstration nano size particles of the present invention.
Fig. 9 is for showing the figure of the blender be used to make negative pole of the present invention.
Figure 10 is for showing the figure of the coating machine be used to make negative pole of the present invention.
Figure 11 is the XRD analysis result of the nano size particles of embodiment 1.
(a) of Figure 12 is that BF-STEM photo, (b) of the nano size particles of embodiment 1 is the HAADF-STEM photo of the nano size particles of embodiment 1.
(a) of Figure 13 is that the nano size particles of embodiment 1 is the EDS collection of illustrative plates of the same visual field at the HAADF-STEM of the 1st observation place photo, (b)～(c).
(a) of Figure 14 is that the nano size particles of embodiment 1 is the EDS collection of illustrative plates of the same visual field at the HAADF-STEM of the 2nd observation place photo, (b)～(c).
Figure 15 is the binary system state diagram of Fe and Si.
Figure 16 is the XRD analysis result of the nano size particles of embodiment 2.
The (a) and (b) of Figure 17 are the STEM photo of the nano size particles of embodiment 2.
(a) of Figure 18 is that the nano size particles of embodiment 2 is the EDS collection of illustrative plates of the same visual field at the HAADF-STEM of the 1st observation place photo, (b)～(d).
(a) of Figure 19 is that the nano size particles of embodiment 2 is the EDS collection of illustrative plates of the same visual field at the HAADF-STEM of the 2nd observation place photo, (b)～(d).
Figure 20 is the XRD analysis result of the nano size particles of embodiment 3.
(a) of Figure 21 is that BF-STEM photo, (b) of the nano size particles of embodiment 3 is the HAADF-STEM photo of the same visual field.
(a)～(c) of Figure 22 is the high-resolution TEM photo of the nano size particles of embodiment 3.
(a) of Figure 23 is that HAADF-STEM figure, (b)～(c) of the nano size particles of embodiment 3 is the EDS collection of illustrative plates of the same visual field.
Figure 24 is the XRD analysis result of the nano size particles of embodiment 4.
(a) of Figure 25 is that BF-STEM photo, (b) of the nano size particles of embodiment 4 is the HAADF-STEM photo of the nano size particles of embodiment 4.
(a)～(b) of Figure 26 is the HAADF-STEM photo of the nano size particles of embodiment 4.
(a) of Figure 27 is that HAADF-STEM photo, (b)～(e) of the nano size particles of embodiment 4 is the EDS collection of illustrative plates of the same visual field.
(a) of Figure 28 is that EDS collection of illustrative plates, (b) of the nano size particles of embodiment 4 is the HAADF-STEM photo of the same visual field.
(a) of Figure 29 is that HAADF-STEM photo, (b) of the nano size particles of embodiment 4 is the EDS analysis result at the 3rd place in (a) for EDS analysis result, (c) at the 1st place in (a) for EDS analysis result, (d) at the 2nd place in (a).
Figure 30 is the figure of the relation of the period of the rechargeable nonaqueous electrolytic battery that shows embodiment and comparative example and discharge capacity sustainment rate.
Embodiment
Below describe embodiments of the present invention in detail based on accompanying drawing.
(the 1. formation of rechargeable nonaqueous electrolytic battery)
The rechargeable nonaqueous electrolytic battery of an embodiment of the present invention at first, is described with reference to Fig. 1.
Rechargeable nonaqueous electrolytic battery 1 of the present invention have can embed and the positive pole 3 of removal lithium embedded ion, can embed and the negative pole 5 of removal lithium embedded ion and be disposed at anodal 3 with negative pole 5 between dividing plate 7, and anodal 3, negative pole 5, reach dividing plate 7 and be arranged in the non-aqueous electrolyte 8 with lithium-ion-conducting.
The invention is characterized in, in negative pole 5, as active material, the particle that uses the element of the lithium ion that constitutes by easy embedding characteristic to form, and the electrolyte 8 of corresponding this negative pole use contains have unsaturated bond and organic substance that can reductive polymerization in molecule.
(2. negative pole)
(formation of the negative electrode active material A of 2-1. the 1st execution mode)
To this, the limit illustrates the 1st execution mode of negative electrode active material of the present invention with reference to Fig. 2 limit.Fig. 2 is the schematic diagram of an example of the formation of demonstration negative electrode active material, and negative electrode active material comprises the 1st particle 9 that contains element X and the 2nd particle 10 that contains element M.
The 1st particle 9 can be formed by the monomer of element X, also can be formed by the solid solution that with element X is principal component.Herein, element X is selected from a kind of element in the group of being made up of Si, Sn, Al, Pb, Sb, Bi, Ge, In, Zn.In addition, be meant that with element X " being principal component " ratio of element X is more than the 50 atom %, more preferably more than the 70 atom %.Be that element X can select from the element of enumerating the group of described element X with the element that forms solid solution, but also can select its epigenesist under the situation of solid solution of element X at the 1st particle 9.Element X is the element that embeds lithium easily, so the 1st particle 9 also can embed lithium.In addition, the 1st particle 9 basically can be for roughly spherical, then is detailed later as for the scheme of other variety of way.
In addition, in the 1st particle 9, from the aspect of the embedding characteristic of lithium ion, element X is preferably Si.In this case, by adding phosphorus or boron, can improve the conductivity of silicon to silicon.Can use indium or gallium to replace phosphorus, also can use arsenic to replace boron.The conductivity of the silicon by improving the 1st particle 9, the internal resistance of negative pole 5 diminishes, and the big electric current that can circulate can show good higher efficiency.
The 2nd particle 10 can be formed by the monomer of element M, also can be by the compound by principal component is formed with the element M.Herein, element M is at least a kind of element that is selected from the group of being made up of the transition metal of the 4th～11 family of periodic table, for example the stable element in the transition metal of the 4th～11 family is specially Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zr, Nb, Mo, Ru, Rh, Pd, Ag, Hf, Ta, W, Re, Os, Ir, Pt, Au etc.These element M are for being difficult for embedding the element of lithium.Do not have special restriction for element, can be described element X yet with element M formation compound.The 2nd particle 10 shows that hardly lithium embeds characteristic, can adjust lithium and embed characteristic according to the ratio of element M, the element of formation compound.In addition, compound can contain various alloys, intermetallic compound, oxide etc.
Therefore and among the present invention, the 2nd particle 10 is formed by the monomer or the compound of element M, has a plurality of electronics more than 2 at the d electron orbit.For example, the outermost electron of Ti, Fe, Ni is configured to Ti:3d[2] 4S[2], Fe:3d[6] 4S[2], Ni:3d[8] 4S[2], 2,6,8 electronics are arranged respectively on the d electron orbit.Can think; by in this kind negative electrode active material, there being a plurality of d electronics; by the interaction of its electronics, what comprised in the non-aqueous electrolyte 8 described later has unsaturated bond and an organic substance generation polymerization that can reductive polymerization in molecule, thereby promotes the formation of the epithelium of protection negative pole 5.In addition, for example, compare as the situation of element M with using Ti, under the situation as element M of using Fe or Ni, can confirm the formation that has promoted overlay film, the therefore measurable many persons of electron number to the d electron orbit are preferred.
In such negative electrode active material of the present invention, shown in the A among Fig. 2, the 1st particle 9 and the 2nd particle 10 are configured to the surface spacing of immediate the 1st particle 9 and the 2nd particle 10 from 1 μ m.In 1 μ m of distance A, be the 1st particle 9 and the 2nd particle 10 the interface electronics interaction can and scope, be the distance of the thickness degree of electric double layer.By when the element X of the 1st particle 9 embeds lithium, simultaneously the element M of the 2nd particle 10 is supplied with electronics, thereby comprised in the non-aqueous electrolyte 8 in molecule, have unsaturated bond and an organic substance generation polymerization that can reductive polymerization.Further, if the distance of the 1st particle and the 2nd particle is in 1 μ m, then the 1st particle is except the reduzate that is created on self surface is coated with, and the more stable reduzate that the 2nd particle generated is adsorbed in the 1st particle surface and clad surface, and electrolytical thus decomposition is suppressed.
In addition, the average grain diameter of the 1st particle 9 is preferably 2nm～500nm, more preferably 2nm～300nm, 50nm～200nm more preferably.According to Hall-Page (Hall-Petch) law, if the little then high yield stress of particle size, if therefore the average grain diameter of nano size particles is about 2nm～500nm, then particle size, yield stress are big, difficultly because of discharging and recharging micronizing take place.In addition, become difficulty if average grain diameter less than 2nm, is then used behind the synthesis of nano sized particles, greater than 500nm, then particle size is excessive, can't obtain sufficient yield stress as if average grain diameter, and is therefore not preferred.
And the 2nd particle 10 can not considered micronized influence, so its average grain diameter can be 2nm～10 μ m.The reason that with 2nm is lower limit is, because this value is the desired value of similarly having no problem in the use with the situation of above-mentioned the 1st particle 9, with 10 μ m is that the reason of the upper limit is, cycle characteristics is reduced.In addition, if the 2nd particle 10 becomes excessive, then the surface area of per unit weight can diminish, and catalytic action also diminishes, and therefore, needs the 2nd a large amount of particles 10 when wanting to obtain effect, thereby cause cell integrated weight to increase, consider that from this aspect the particle size of the 2nd particle 10 is preferred with little.
In the negative pole of the present invention 5 like this, ratio with respect to the 2nd particle 10 of the 1st particle 9, can utilize the 1st particle 9 can guarantee to set arbitrarily in the scope of desired lithium embedded quantity, as standard roughly, atomicity with respect to the X that constitutes the 1st particle 9, be preferably 1%～30%, more preferably 7%～10%.If atomicity less than 1%, then can't obtain on the sufficient negative terminal surface film-formation result and when discharging and recharging the inhibition effect of the change in volume of subsidiary negative pole.If it is not atomicity greater than 30%, then has the possibility that can't guarantee sufficient lithium embedded quantity, therefore preferred.
(effect of 2-2. negative electrode active material A)
Negative pole according to the 1st execution mode, except the 1st particle 9 that embeds lithium, also comprise the 2nd particle 10 that does not embed lithium, can be by the catalytic action of the 2nd particle 10, what form effectively on the surface of negative electrode active material layer that non-aqueous electrolyte 8 described later comprised has unsaturated bond and an organic stable overlay film that can reductive polymerization in molecule, thereby make negative electrode active material stable, can prevent that electrolyte from decomposing, and can obtain the negative pole of cell excellent in cycle characteristics.
In addition, as negative electrode active material, except the 1st lower particle 9 of conductivity, also has under the situation of the 2nd particle 10 that comprises the high element M of conductivity the rapid rising of conductance of negative pole 5 integral body.That is to say, even conductive auxiliary agent also is to have the conductivity negative electrode active material less, thereby can form the electrode of high power capacity, and can become the negative electrode active material of high magnification characteristic good.Particularly, by using metallic elements such as high Fe of conductivity or Cu, can obtain and only compare the better negative electrode active material of conductivity for the situation of silicon nano etc. as the 2nd particle 10.
Further,, except the 1st particle 9, also comprise the 2nd particle as negative electrode active material, the volumetric expansion when embedding lithium of the 1st particle 9, relative therewith, the 2nd particle 10 does not embed lithium, thereby can suppress the variation of negative pole overall volume.Thus, even embed lithium, also can relax the distortion that the volumetric expansion of negative pole is followed, the reduction of the discharge capacity when suppressing cycle characteristics.
(formation of the negative electrode active material B of 2-3. the 2nd execution mode)
Then, the 2nd execution mode to negative electrode active material of the present invention describes.Fig. 3 is the summary sectional view of the nano size particles 11 of the negative electrode active material of demonstration formation negative pole 5 of the present invention.Nano size particles 11 containing element X and element M.
Identical with the 1st above-mentioned execution mode, element X is the a kind of element that is selected from the group of being made up of Si, Sn, Al, Pb, Sb, Bi, Ge, In, Zn.Element X is the element that embeds lithium easily.
In addition, element M is at least a kind of element that is selected from the group of being made up of the transition metal of the 4th～11 family, be element stable in the transition metal of the 4th～11 family for example, be specially Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zr, Nb, Mo, Ru, Rh, Pd, Ag, Hf, Ta, W, Re, Os, Ir, Pt, Au etc.These element M are for being difficult for embedding the element of lithium.
And the nano size particles 11 among the present invention has the 1st mutually 13 and the 2nd mutually 15 at least.
The 1st 13 can be the monomer of element X mutually, also can be to be the solid solution of principal component with Si.In addition, the 1st phase 13 can be that crystalline also can be a noncrystalline.Become element that the element of solid solution can be enumerated from the group of element X to select in the epigenesist with the element X-shaped.The 1st 13 can embed lithium mutually.In a single day the 1st mutually 13 embed lithium and after the alloying, breaks away from lithium and carry out removal alloying and then become noncrystalline.
In addition, the 2nd mutually 15 can be the monomer of element M or also can be to be the compound of principal component with the element M.The 2nd 15 embeds lithium mutually hardly.And, as mentioned above,, thereby can promote to protect the formation of the epithelium of negative pole 5 because element M has a plurality of electronics more than 2 at the d electron orbit, improve cycle characteristics.
If element X and element M are for can form combination of compounds, then the 2nd mutually 15 can be by MX as the compound of element X and element M YDeng formation.On the other hand, if element X and element M are for can't form combination of compounds, then the 2nd mutually 15 can be the monomer of element M or solid solution etc.
For example, be that Si, element M are under the situation of Cu at element X, the 2nd 15 can be formed by the copper silicide as the compound of element M and element X mutually.For example, be that Si, element M are under the situation of Ag or Au at element X, the 2nd 15 can be that the solid solution etc. of principal component forms by the monomer of element M or with the element M mutually.
In addition, be under the situation of Si at element X, Si and element M can form with MX YThe compound of (1＜Y≤3) expression.As such compound, for example specifically can illustration FeSi 2, CoSi 2, or NiSi 2(Y=2), Rh 3Si 4(Y=1.33), Ru 2Si 3(Y=1.5), Sr 3Si 5(Y=1.67), Mn 4Si 7Or Tc 4Si 7(Y=1.75), IrSi3 (Y=3) etc.Herein, the atom ratio of shared element M is preferably 0.01～25% in the total of Si and element M.If this atom ratio is 0.01～25%, then can when using nano size particles 11, take into account cycle characteristics and high power capacity as negative electrode active material.On the other hand,, then can't suppress the change in volume of nano size particles 11 when embedding lithium, the advantage of high power capacity is disappeared if surpass 25% if be lower than 0.01%.
And nano size particles 11 is for example shown in Figure 3, the 1st mutually 13 with the 2nd mutually 15 both be exposed to the outer surface of nano size particles 11, and be bonded with each other by the interface.The 1st mutually 13 with the 2nd mutually 15 interface be plane or curved surface.In addition, the interface also can be for stepped.The 1st mutually 13 outer surface be dome shape roughly.The 1st mutually 13 with the 2nd mutually the interface shape at 15 junction surface become circle or ellipse.By on the 1st phase 13 that expands because of the embedding lithium, there being the 2nd phase 15 that does not embed lithium, can suppress to embed the expansion of the 1st phase 13 that is produced because of lithium.
In addition, the 1st mutually 13 outer surface be dome shape roughly, be meant except that with the 1st mutually 13 with the 2nd mutually the surface of the 1st phase 13 15 interfaces that contacts with level and smooth substantially curved surface formation, in other words, be meant the 1st mutually 13 with the 2nd (Japanese: earlier), the 1st phase 13 is a sphere or oval with the tip in 15 contact positions mutually.The lexical representation of ball or oval ball is not meant that tight geometrically sphere is with oval spherical.It is with as to utilize being shaped as of particle that crush method forms variform shape representative, that the angle is arranged on the surface.
In addition, the nano size particles 11 shown in Fig. 3 (b) is such, also can be scattered in the 1st phase 13 as the monomer of element M or the 2nd phase 15 of compound.The 2nd phase 15 is covered by the 1st phase 13.Be exposed to outer surface the 2nd 15 same mutually, the 2nd 15 embeds lithium mutually hardly.In addition, shown in Fig. 3 (c), can be exposed to the surface by the part of the 2nd phase 15 of the 1st phase 13 coverings.That is to say, not necessarily need all 13 being covered with mutually of the 2nd phase 15 on every side, also can 13 only cover the 2nd phase 15 part on every side mutually by the 1st by the 1st.
In addition, among Fig. 3 (b), though a plurality of the 2nd phases 15 that in the 1st phase 13, are scattered here and there, in the 2nd phase 15 that also can be single is included in.
The 2nd phase 15 ' shown in Fig. 4 (a) is such, because the influence of the stability of the crystal of the monomer of element M or compound etc. forms polyhedron-shaped sometimes.
Further, the nano size particles 11 shown in Fig. 4 (b) is such, can have a plurality of the 2nd phases 15 on the 1st phase 13.For example, in the manufacture process of particle, can consider following situation: the situation that the ratio of element M is few, the element M frequency of collisions each other when gaseous state or liquid condition tails off; Because the influence of relation, wetability and the cooling rate of the fusing point of the 1st phase the 13 and the 2nd phase 15 etc., the 2nd phase 15 is scattered in the also situations of joint of the 1st phase 13 surfaces.
Have mutually a plurality of the 2nd on 13 mutually under 15 the situation the 1st, the 1st mutually 13 with the 2nd mutually the area at 15 interface become big, thereby can further suppress the expansion contraction of the 1st phase 13.In addition, the 2nd mutually 15 since conductance than the 1st 13 height mutually, thereby with the 2nd 15 promotion movement of electrons mutually, nano size particles 11 becomes and has a plurality of current collection points in each nano size particles 11.Therefore, the nano size particles 11 with a plurality of the 2nd phases 15 becomes the negative material with high powder conductance, can reduce conductive auxiliary agent, can form the negative pole of high power capacity.And then, can obtain the negative pole of high magnification characteristic good.
Comprise be selected from by in the group of selective elements M more than 2 kinds under the situation of element as element M, containing another element M with solid solution or compound form in 15 mutually as the 2nd of the compound of some element M and element X sometimes.That is to say, be selected from by under the situation of element more than 2 kinds in the group of selective elements M, sometimes element M as described later even in nano size particles, comprise ' like that, do not form other the 2nd mutually 19.Be that Si, an element M are that Ni, another element M are under the situation of Fe at element X for example, Fe is present in NiSi with the solid solution form sometimes 2In.In addition, when observing with EDS, the distribution of existing Ni and the roughly the same situation of the distribution of Fe have different situations again, thereby another element M is comprised in the 2nd phase 15 sometimes equably, and also part is comprised in the 2nd phase 15 sometimes.
In addition, nano size particles can also containing element M ' except element M.Element M ' for being selected from least a kind of element in the group of forming by Cu, Fe, Co, Ni, Ca, Sc, Ti, V, Cr, Mn, Sr, Y, Zr, Nb, Mo, Tc, Ru, Rh, Ba, lanthanide series (except Ce and Pm), Hf, Ta, W, Re, Os, Ir, for formation the described the 2nd different types of element of element M mutually.
Nano size particles 17 containing element M and element M shown in Fig. 5 (a) ', except as the 2nd mutually 15 of the monomer of element M or compound, also have another the 2nd mutually 19.For example, the 1st mutually an end of 13 have the 2nd mutually 15, the other end have another the 2nd mutually 19, nano size particles 17 can have the shape at two beads of surface engagement of big ball.Another the 2nd 19 is an element M mutually ' monomer or compound, 15 similarly embed lithium hardly mutually with the 2nd.In addition, nano size particles 17 also can comprise by element M and element M ' solid solution (not shown) that constituted.For example can enumerate following situation etc.: the 2nd mutually 15 is the compounds of Si with Fe, and another the 2nd phase 19 is the compound of Si and Co, element M and element M ' formed solid solution is the solid solution of Fe and Co.
In addition, shown in Fig. 5 (b), as the monomer of element M or compound the 2nd mutually 15, as and element M ' monomer or another of compound the 2nd 19 also can be scattered in the 1st phase 13 mutually.In addition, Fig. 5 (a) is though and (b) illustrate from selective elements M and element M ' the group of element select the example of the situation of 2 kinds of elements, also can select element more than 3 kinds.
In addition, like this from element M and element M ' group select under the situation of element more than 2 kinds, the atom ratio of the total of the element of the group of ' the total of element of group, element M and element M ' also is preferably 0.01～30% with respect to element X and element M and element M.
In addition, among the present invention, the preferred the 1st 13 is mainly crystalline silicon mutually, and the 2nd phase 15 is the crystal silicide.In addition, the 1st phase 13 has more preferably been added the Si of phosphorus or boron.Can improve the conductivity of silicon by interpolation phosphorus or boron.Can use indium or gallium to replace phosphorus, also can use arsenic to replace boron.By improving the 1st conductivity of 13 silicon mutually, thereby used the internal resistance of the negative pole of such nano size particles to diminish, the big electric current that can circulate has good high magnification characteristic.
And then in the present invention, nano size particles 11 and 17, described later 21 average grain diameter are preferably 2～500nm, 50～200nm more preferably.According to Hall-Page law, if the little then high yield stress of particle size, if therefore the average grain diameter of nano size particles is 2～500nm, then particle size is fully little, yield stress is fully big, difficultly because of discharging and recharging micronizing takes place.In addition, become difficulty if average grain diameter less than 2nm, is then used behind the synthesis of nano sized particles, greater than 500nm, then particle size is excessive as if average grain diameter, and yield stress is insufficient.
In addition, because particulate condenses existence usually, thereby the average grain diameter of nano size particles is meant the average grain diameter of primary particle at this.For the instrumentation of particle, merge the image information of use electron microscope (SEM) and the volume reference median particle diameter of dynamic light scattering luminance meter (DLS).Average grain diameter can be confirmed shape of particle, be asked for particle diameter with image analysis (for example Engineering of Asahi Chemical Industry system " Azokun " registered trade mark) by the SEM image in advance; Perhaps particle being scattered in solvent, utilizing DLS (for example, big tomb electronics system DLS-8000) measures etc.If microparticulate fully and is not condensed, then can obtain roughly the same measurement result with SEM and DLS.In addition,, under the situation that is shaped as planform highly developed as acetylene black of nano size particles, also, can ask for average grain diameter herein by the image analysis of SEM photo with primary particle size definition average grain diameter.
In addition, also can be the most surperficial of nano size particles 11 or 17 in conjunction with aerobic.This be because, if nano size particles is fetched in the air, then airborne oxygen can with the element reaction on nano size particles surface.That is to say, nano size particles 11 or 17 the most surperficial to have thickness be unformed layer about 0.5～15nm, it is inferior particularly to be mainly the situation of crystalline silicon mutually the 1st, also can have oxidation film layer.
(effect of 2-4. negative electrode active material B)
According to the 2nd execution mode, except the 1st phase 13 that embeds lithium, also has the 2nd phase 15 that contains element M, therefore with the 1st execution mode similarly, can be by the 2nd 15 catalytic action mutually, form organic stable overlay film effectively on the surface of negative electrode active material layer, can prevent the decomposition of electrolyte, improve cycle characteristics.
In addition, the 1st 13 volumetric expansions when embedding lithium mutually, but the 2nd phase 15 does not embed lithium, thereby can suppress and the 2nd 15 the 1st 13 the expansions mutually of joining mutually.That is to say, though the 1st mutually 13 desires embed lithium and make volumetric expansion, the 2nd 15 also is difficult to expand mutually, thereby the 2nd effects of 15 performances as wedge or pin mutually, the expansion of inhibition nano size particles 11 or 17 integral body.Therefore, with do not have the 2nd mutually 15 particle compare, have the 2nd mutually 15 nano size particles 11 or 17 when embedding lithium, be difficult for expanding, restoring force works and gets back to shape originally easily when removal lithium embedded.Therefore, according to the present invention, even nano size particles 11 or 17 embeds lithium, also can relax the distortion that volumetric expansion is followed, the discharge capacity when suppressing cycle characteristics reduces.
Further, according to the 2nd execution mode, nano size particles 11 or 17 be difficult for to expand, even therefore nano size particles is taken out in the atmosphere, also be difficult for atmosphere in the oxygen reaction.On the other hand, only have the nano size particles of either party's phase, then can carry out oxidation by the surface toward particle inside, therefore make the whole oxidation of nano size particles from surface and oxygen reaction if under the situation of not protecting the surface, be positioned in the atmosphere.Yet under with nano size particles 11 of the present invention or 17 situations about being positioned in the atmosphere, though particle is the most surperficial and oxygen reacts, nano size particles is whole to be difficult for expansion, so the difficult intrusion of oxygen is inner, and is difficult to the central part that oxidation reaches nano size particles.Therefore, common metal nanoparticle is because of the big oxidation easily of specific area, generation heating or volumetric expansion, but nano size particles 11 of the present invention or 17 need not carried out special surface coated with organic substance or metal oxide, can use with the powder former state in atmosphere.Such feature is big in industrial value.
In addition, according to the 2nd execution mode, the 2nd 15 containing element M mutually, so conductivity height, though have comprise the low element X of conductivity the 1st mutually 13 as principal phase, the also rapid rising of the conductance of nano size particles 11 or 17 integral body.If change a view, nano size particles 11 or 17 is equal to the structure that has the current collection point of nano-scale in each nano size particles, even conductive auxiliary agent also becomes the negative material with conductivity less, the electrode of high power capacity can be formed, and the negative electrode active material of high magnification characteristic good can be obtained.Particularly by mutually using metallic elements such as high Fe of conductivity or Cu in 15 the 2nd, compare with the situation of independent silicon nano etc., can obtain high conductive negative electrode active material.
In addition, for the 1st comprise in 13 mutually the 2nd mutually 15 nano size particles 11, the 1st comprise in 13 mutually the 2nd mutually 15 with another the 2nd mutually for 19 the nano size particles 17, the 1st mutually 13 than many parts with do not embed joining of lithium, can more effectively suppress the expansion of the 1st phase 13.Its result, nano size particles 17 can suppress the effect of volumetric expansion with a spot of element M performance, can effectively increase the amount of the element X such as Si that can embed lithium, the high and raising cycle characteristics of capacity.
Possess be exposed to outer surface the 2nd mutually 15 with another the 2nd mutually 19 the two nano size particles 17 not only have and above-mentioned same effect, and the current collection point of nano-scale increase, current collection performance is improved effectively.If add element M and element M more than 2 kinds ' the element of group, then generate compound more than 2 kinds, these compounds are separated from each other easily thereby different compounds separates easily, so current collection point increase easily, thereby more preferably.
(formation of the negative electrode active material C of 2-5. the 3rd execution mode)
Further the nano size particles 21 to the 3rd execution mode of negative pole 5 of the present invention describes.To indicating identical numbering, and avoid repeat specification in the following execution mode with key element that the 2nd execution mode is finished same mode.
Fig. 6 is the summary sectional view of the nano size particles 21 of the negative electrode active material of formation negative pole 5 of the present invention.Shown in Fig. 6 (a), nano size particles 21 as hereinbefore, except the 1st mutually 13, and the 2nd mutually 15, further have the 3rd mutually 23.The 3rd 23 containing element X ' mutually, it is at least a kind of element that is selected from the group of being made up of Si, Sn, Al, Pb, Sb, Bi, Ge, In and Zn, for the different types of element of element X.These elements X ' is the element that easily embeds lithium.The 3rd mutually 23 can be the monomer of element X ', also can be for being the solid solution of principal component with element X '.The element that forms solid solution with element X ' can be the element of selecting from the group of selective elements X ', also can be the element of not enumerating in described group.The 3rd 23 can embed lithium mutually.
The 1st mutually the 13, the 2nd mutually 15, and the 3rd 23 all be exposed to outer surface mutually, the 1st mutually the 13, the 2nd mutually 15, and the 3rd mutually 23 outer surface can be ball shape roughly.The 2nd 15 13 engage mutually mutually, the 3rd 23 be bonded with each other mutually by in interface and the 1st phase the 13 and the 2nd phase 15 at least one with the 1st.For example, the 1st mutually an end of 13 have the 2nd mutually 15, have the 3rd mutually 23 at the other end, nano size particles 21 can have the shapes with two little ball bond on big ball surface.The 3rd mutually 23 with the 1st 13 interface display plane or curved surface mutually.On the other hand, shown in Fig. 7 (a), the 2nd mutually 15 and the 3rd mutually 23 also can be by interface.
For such nano size particles 21, embed characteristic and conductivity etc. if consider the lithium of negative electrode active material, then illustration for example have the 1st mutually 13 for Si, the 2nd mutually 15 for the compound, the 3rd of Si and Fe 23 be Sn etc. mutually.
In addition, the nano size particles 21 shown in Fig. 6 (b) is such, as the monomer of element M or compound the 2nd mutually 15, and 23 also can be scattered in the 1st mutually in 13 mutually as the 3rd of the monomer of element X ' or solid solution.In addition, also can disperse with (not shown) mutually of the compound of element M by element X '.Though these phases 15,23 are covered by the 1st phase 13, shown in Fig. 6 (c), the phase 15,23 of a part also can be exposed to the surface.That is to say, do not need and mutually 13 to cover and be scattered in the 1st mutually around the phase 15,23 in 13 whole with the 1st, also can the 1st 13 only cover a part on every side mutually.In addition, mutually can be dispersed with a plurality of phases in 13 the 1st, for example can be dispersed with the 2nd mutually the 15, the 3rd mutually 23, as the compound of element X ' and element M mutually in any one.
In addition, 3rd phase 23 of the shape on the surface beyond the interface of the 3rd phase 23 shown in Fig. 6 (a) is such, can be the roughly level and smooth sphere in surface, and the 3rd phase 23 ' shown in Fig. 7 (b) like that, also can be for polyhedron-shaped.Polyhedron-shaped in nano size particles 11,17 or 21 by the 3rd mutually 23 engaging the back, peeling off and produce.
In addition, the 1st mutually the 13 and the 3rd 23 can suppress position with the lithium reaction by comprising oxygen mutually.Though capacity reduces when comprising oxygen, can suppress to embed the volumetric expansion that lithium is followed.The addition z of oxygen for example is being XO z, X ' O zThe time, the scope of preferred 0＜z＜1.If z is more than 1, then the Li embedded location of element X and element X ' is suppressed, and capacity declines to a great extent.
At nano size particles containing element X, element X ', element M, and the atom ratio of element M ' situation under, shared element M and element M in the total about them ', the reason according to same as described above is preferably about 0.01～25%.If this atom ratio is 0.01～25%, then when using nano size particles 21, can take into account cycle characteristics and high power capacity as negative electrode active material.
In addition, about the formation of nano size particles 21 of the present invention, can consider other variety of way.For example, can have a plurality of the 3rd phases 23 on the surface of the 1st phase 13.In addition, for example, nano size particles 21 can further contain the element X ' more than 2 kinds.For example, the 2nd kind of element X ' be for to be selected from by a kind of element in the group of described element X ', for the 1st kind of different types of element of element X '.For example,, can use silicon as element X, and, as element X ', can use tin, aluminium.Element X ' can form another the 3rd phase with monomer or solid solution form, also can formation and element M and element M ' etc. compound.Another is the 3rd 23 same mutually with the 3rd, and outer surface is a dome shape, can be exposed to the outer surface of nano size particles 21.In addition, also can be scattered in the 1st mutually mutually the 13 or the 3rd mutually in 23 as the compound of element X ' and element M.Further, nano size particles 21 can also containing element M ' except element M.
Like this, nano size particles 21 can according to the element of the group of the element of the group of element X, X ', element M, and element M ' the various combinations of element of group comprise the compound of multiple composition, the phase of solid solution.Such phase can be exposed to the surface of nano size particles 21, perhaps also can be scattered in the 1st mutually 13 or other arbitrarily mutually in.
In addition, also can tie and aerobic the most surperficial of nano size particles 21.This be because, if nano size particles is fetched in the air, then airborne oxygen can with the element reaction on nano size particles 21 surfaces.That is to say that it is unformed layer about 0.5～15nm that nano size particles 21 the most surperficial has thickness, it is inferior particularly to be mainly the situation of crystalline silicon mutually the 1st, also can have oxidation film layer.
(effect of 2-6. negative electrode active material C)
According to the 3rd execution mode, can obtain the effect identical with the effect of the 2nd execution mode gained.But, according to the 3rd execution mode, the 1st 13 volumetric expansions when embedding lithium mutually, the 3rd phase 23 also expands when embedding lithium.Yet, the 1st mutually 13 with the 3rd mutually in 23, embed the electrochemical current potential difference of lithium, therefore, one preferentially embeds lithium mutually, and when a phase volume expansion, the volumetric expansion meeting of another phase tails off relatively, thus this is difficult for volumetric expansion mutually because of another phase.Therefore, with do not have the 3rd mutually 23 o'clock particle compare, have the 1st mutually 13 with the 3rd nano size particles 21 difficult expansion when embedding lithium of 23 mutually.Therefore,,, nano size particles 21 also can suppress volumetric expansion even embedding lithiums according to the 3rd execution mode, thus the reduction of the discharge capacity when suppressing cycle characteristics.
(alternate manner of 2-7. negative electrode active material)
In addition, as negative electrode active material of the present invention, the 1st particle 9 among the above-mentioned negative electrode active material A also can use the nano size particles of above-mentioned negative electrode active material B and C.By doing like this, negative electrode active material A can further obtain and negative electrode active material B and the same effect of C.
Further, as negative electrode active material of the present invention, can consider following material, it utilizes for example copper, tin, zinc, silver, nickel or carbon to coat at least a portion on the surface of the 1st particle 9 among above-mentioned negative electrode active material A～C, nano size particles 11,17,21.The thickness that coats is illustrated as the scope of 0.01～0.5 μ m.For example, such formation also can be understood as, and in the nano size particles 17 shown in Figure 5, selects Cu as element M ', as element M ' monomer another the 2nd mutually 19 not with the 1st 13 surface engagement mutually, and to cover the 1st the 13 and the 2nd 15 form (not shown) existence mutually mutually.
Coated by the good material of conductivity by the surface of negative electrode active material like this,, also can improve the negative pole monolithic conductive, and improve cycle characteristics even do not use conduction not help material etc.In addition, because the surface of negative electrode active material coated, thereby can suppress the oxidation of silicon etc.By clad surface, aspect the change in volume that produces discharging and recharging on also patience improve.
(manufacture method of 2-8. nano size particles)
The manufacture method of nano size particles is described herein.
Nano size particles can utilize gas phase synthesis method to synthesize.Particularly, with the material powder plasmaization, be heated to and be equivalent to 10,000 K, cooling can be made nano size particles thus thereafter.
Below based on Fig. 8 one concrete example of employed manufacturing installation when making nano size particles is described.In the nano size particles manufacturing installation 37 shown in Figure 8, on the external wall of upper portion of reative cell 39, be wound with and produce the high frequency coil 46 that plasma is used.High frequency coil 46 usefulness high frequency electric sources 47 are applied the alternating voltage of several MHz.Preferred frequency is 4MHz.In addition, the external wall of upper portion of twining high frequency coil 46 forms the columnar bimetallic tube that is made of quartz glass etc., flows through cooling water betwixt in the crack to prevent the fusion of the quartz glass due to the plasma.
In addition, on the top of reative cell 39, be provided with material powder supply port 41 and protective gas supply port 43.The material powder of being supplied with by the material powder dispenser 42 is supplied in the plasma 49 by material powder supply port 41 with carrier gas 45 (rare gas such as helium, argon).In addition, protective gas 44 can be supplied to reative cell 39 by protective gas supply port 43.In addition, material powder supply port 41 does not need necessarily to be arranged at as shown in Figure 8 the top of plasma 49, also can be at plasma 49 nozzle transversely is set.In addition, also can use cooling water water-cooled material powder supply port 41.In addition, the proterties of raw material that is supplied to the nano size particles of plasma is not only limited to powder, slurries or gasiform raw material that can the base feed powder yet.
The effect of the dispersion of the pressure of reative cell 39 performance maintenance plasma reaction portions, the micropowder of inhibition manufacturing.Reative cell 39 gives water-cooled in order to prevent the damage that plasma causes.In addition, be connected with suction tube, be provided with the filter 51 that is used to capture the micropowder that is synthesized midway at this suction tube at the sidepiece of reative cell 39.The suction tube that links reative cell 39 and filter 51 also gives water-cooled with cooling water.Pressure utilizations in the reative cell 39 are arranged at the attraction power of not shown vacuum pump VP in the downstream of filter 51 and adjust.
The manufacture method of nano size particles is for becoming the method from bottom to top that solid is separated out nano size particles by plasma through gas, liquid, become in the drop stage spherical, thereby the 1st mutually 13 with the 2nd mutually 15 become spherical.On the other hand, according to the method from top to bottom that macroparticle is diminished as crush method or mechanochemical reaction, the shape of particle becomes unsmooth, and is different greatly with the shape of the sphere of nano size particles 11.
In addition, if in material powder, use the mixed-powder of element X and element M powder separately, then can obtain the nano size particles 11 of the 2nd execution mode.On the other hand, if in material powder, use element X, element M, element M ' mixed-powder of separately powder, then can obtain the nano size particles 17 of the 2nd execution mode.In addition, if in material powder, use element X, element M (and element M '), with the mixed-powder of element X ' powder separately, then can obtain the nano size particles 21 of the 2nd execution mode.
About the 1st particle, the 2nd particle of the 1st execution mode, can utilize above-mentioned nano size particles manufacturing installation and method to make, also can use well known the whole bag of tricks to make.
In addition, be not particularly limited, can adopt well known the whole bag of tricks for the gimmick on coating particles surface.When clad metal, can use electroless plating or displacement plating, under little at the surface oxidation of particles such as silicon, as the to have conductivity situation, also can be with electroplating.When carbon coated, can use after the carbon source of organic systems such as inorganic systems such as mixed carbon black or polyvinyl alcohol heat-treating methods etc. in torpescence or reproducibility environment.In addition, also can utilize thermal decomposition CVD method etc., thermal decomposition CVD method is by making its thermal decomposition with more than the hydrocarbon system gas heated to 600 ℃, thereby particle surface applied the coating of carbon.
(manufacture method of 2-9. negative pole)
Next the manufacture method of anode for nonaqueous electrolyte secondary battery is described.Negative pole of the present invention can be coated collector body and drying forms by the coating fluid that will comprise negative electrode active material, electric conducting material and binding material at least.For example, as shown in Figure 9, coating fluid can be by preparing slurries raw material 57 input blenders 53 and the mixing slurries (coating fluid) 55 that form.Slurries raw material 57 is nano size particles, conductive auxiliary agent, binding agent, thickener, solvent etc.
For the cooperation of the solid constituent in the slurries 55, general standard can be for example nano size particles 25～90 weight %, conductive auxiliary agent 5～70 weight %, binding agent 1～30 weight %, thickener 0～25 weight %.
Blender 53 can use common mixing roll used in the preparation of slurries, also can use the device that can prepare slurries that is called as kneader, mixer, dispersion machine, mixer etc.In addition, as thickener, the mixture more than a kind or 2 kinds in the polysaccharides such as suitable use carboxymethyl cellulose, methylcellulose etc.In addition, can make water as solvent.In addition, when preparation organic system slurries, can use the N-N-methyl-2-2-pyrrolidone N-as solvent.
Conductive auxiliary agent is the powder that at least a kind of conductive material constituted that selects in the group of compositions such as free carbon, copper, tin, zinc, nickel, silver.Can also can be the powder of each alloy for the powder of the monomer of carbon, copper, tin, zinc, nickel, silver.For example, can use common carbon blacks such as furnace black or acetylene black.And then, can add the nano-sized carbon angle as conductive auxiliary agent.Particularly, be under the situation of the low silicon of conductivity at the element X of nano size particles, silicon is exposed to the surface of nano size particles, the conductivity step-down, therefore preferred interpolation nano-sized carbon angle is as conductive auxiliary agent.Herein, nano-sized carbon angle (CNH) takes graphite film is rounded to conical structure, and actual form is that the aggregate form with following form exists: a plurality of CNH summit is towards the outside, the form as radial sea urchin.The external diameter of the sea urchin shape aggregate of CNH is about 50nm～250nm.Preferred especially average grain diameter is the CNH about 80nm.These materials can use any, also can make up more than 2 kinds and use.
The average grain diameter of conductive auxiliary agent is meant the average grain diameter of primary particle., under the situation of planform highly developed as acetylene black, also can define average grain diameter herein, ask for average grain diameter by the image analysis of SEM photo with primary particle size.
In addition, also can use particle shape conductive auxiliary agent and lead shape conductive auxiliary agent the two.Lead shape conductive auxiliary agent is the lead of conductive material, can use the conductive material of being enumerated in the particle shape conductive auxiliary agent.Lead shape conductive auxiliary agent can use the thread like bodies of external diameter below 300nm such as carbon fiber, carbon nano-tube, copper nm-class conducting wire, nickel nm-class conducting wire.By use lead shape conductive auxiliary agent, thereby be electrically connected with maintenances such as negative electrode active material and collector bodies easily, when improving current collection performance, the negative pole membranaceous in porous increased fibrous material, is difficult for producing slight crack in negative pole.For example can consider to use copper powders may as particle shape conductive auxiliary agent, use lead shape conductive auxiliary agent as vapor deposition carbon fiber (VGCF:Vapor Grown Carbon Fiber).In addition, also can not add particle shape conductive auxiliary agent, and only use lead shape conductive auxiliary agent.
The length of lead shape conductive auxiliary agent is preferably 0.1 μ m～2mm.The external diameter of conductive auxiliary agent is preferably 4nm～1000nm, more preferably 25nm～200nm.If the length of conductive auxiliary agent is that then this length is enough to improve the productivity ratio of conductive auxiliary agent more than the 0.1 μ m,, then be convenient to the coating of slurries if length is below the 2mm.In addition, easily synthetic under the external diameter of the conductive auxiliary agent situation thicker than 4nm, under the external diameter situation thinner than 1000nm, slurries mixing easily.The external diameter of conductive materials and the assay method of length are undertaken by the image analysis based on SEM.
Binding agent is the binding agent of resin, and can use Kynoar fluororesin such as (PVdF), styrene butadiene is organic materials such as cellulose family, polyimides, polyamidoimide such as rubber synthetic rubber such as (SBR), acrylic resin, carboxymethyl cellulose.These materials can use wantonly a kind, also can make up more than 2 kinds and use.
As solvent, can make water or N-N-methyl-2-2-pyrrolidone N-(NMP) etc.
Then, as shown in figure 10, for example use coating machine 59 slurries 55 to be coated on the one side of collector body 61.Coating machine 59 can use the common apparatus for coating that can be coated on slurries 55 collector body 61, for example roll-coater and utilize coating machine, comma coating machine, the die coater of scraper.
Collector body 61 is for being selected from the formed paper tinsel of at least a kind of metal in the group that is made of copper, nickel, stainless steel.Each metal can use separately, also can use with alloy form separately.Thickness is preferably 4 μ m～35 μ m, further is preferably 8 μ m～18 μ m.
, about 50～150 ℃ carry out drying,, can obtain anode for nonaqueous electrolyte secondary battery by roll-in in order to adjust thickness thereafter.When using polyimides or polyamidoimide, further preferably in 250 ℃～450 ℃ scope, carry out heat treated as binding material.
(3. positive pole)
Anodal 3 can use and can embed and the various positive poles of removal lithium embedded ion.This lithium ion battery is with anodal preparing the composition of positive active material by mixed cathode active material, conductive auxiliary agent, binding agent and solvent etc., it directly being coated metal current collector such as aluminium foil and drying is made.
As positive active material, so long as normally used material just can use any, but illustration LiCoO for example 2, LiMn 2O 4, LiMnO 2, LiNiO 2, LiCo 1/3Ni 1/3Mn 1/3O 2, LiFePO 4Deng compound.
Can use for example carbon black as conductive auxiliary agent, can use for example Kynoar (PVdF), water-soluble propenoic-acids adhesive, can use N-N-methyl-2-2-pyrrolidone N-(NMP), water etc. as solvent as binding agent.At this moment, the content of positive active material, conductive auxiliary agent, binding agent and solvent is for being used in the level of rechargeable nonaqueous electrolytic battery etc. usually.
(4. dividing plate)
As dividing plate, so long as have the function of the anodal electrical conductivity with negative pole of insulation, can use in rechargeable nonaqueous electrolytic battery normally used any one.For example can use little porousness polyolefin film.
(5. electrolyte/electrolyte)
As electrolyte and electrolyte, can use non-water system organic electrolyte used, that have lithium-ion-conducting in lithium rechargeable battery, the Li polymer battery etc.
As the concrete example of the solvent of organic electrolyte, can enumerate carbonic esters such as ethylene carbonate, propylene carbonate, butylene carbonate, diethyl carbonate, dimethyl carbonate, methyl ethyl carbonate; Ethers such as diethyl ether, butyl oxide, glycol dimethyl ether, ethylene glycol diethyl ether, butyl cellosolve, diethylene glycol dimethyl ether; Benzonitrile, acetonitrile, oxolane, 2-methyltetrahydrofuran, gamma-butyrolacton, dioxolane, 4-methyl dioxolane, N, non-protonic solvents such as dinethylformamide, dimethylacetylamide, dimethylated chlorobenzene, nitrobenzene are perhaps with the mixed solvent that mixes more than 2 kinds in these solvents.
For the electrolyte of organic electrolyte, can use by LiPF 6, LiClO 4, LiBF 4, LiAlO 4, LiAlCl 4, LiSbF 6, LiSCN, LiCl, LiCF 3SO 3, LiCF 3CO 3, LiC 4F 9SO 3, LiN (CF 3SO 2) 2Deng a kind in the electrolyte that lithium salts constituted or with the person of mixing more than 2 kinds.
And, the invention is characterized in that electrolyte contains have unsaturated bond and organic substance that can reductive polymerization in molecule.By such organic substance is added into electrolyte, can forms effective solid electrolyte interface overlay film on the surface of negative electrode active material, thereby can suppress the decomposition of electrolyte material.As in molecule, have unsaturated bond and when charging can reductive polymerization material, for example except carbonic ester such as fluorinated ethylene carbonate, vinylene carbonate (VC), vinylethylene carbonate and derivative thereof, can use unsaturated carboxylate type, phosphoric acid ester, borate ester, and alcohols etc.Wherein, use vinylene carbonate (VC) to come illustration as preference.
For such organic substance,, preferably add about the 0.1 weight %～10 weight % of electrolyte weight in order to obtain stable solid electrolyte interface overlay film.Further be preferably and add about 1 weight %～5 weight %.If addition in the scope of 0.1 weight %～10 weight %, then can be reduced when charging, form stable overlay film on the surface of negative electrode active material layer, thereby can prevent the decomposition of electrolyte.Under the situation of addition less than 0.1 weight %, be difficult to form stable overlay film fully on the surface of negative electrode active material, in addition, surpass under the situation of 10 weight % at addition, the amount that is reduced increases, therefore formed solid electrolyte interface overlay film thickening causes the impedance of battery to rise, thereby not preferred.
(the 6. assembling of rechargeable nonaqueous electrolytic battery)
Rechargeable nonaqueous electrolytic battery of the present invention forms battery structure by configuration dividing plate between aforesaid positive pole and negative pole.Reel or the such battery structure of folding, put into cylindrical shape or square battery case, inject electrolyte then, finish lithium rechargeable battery.
Particularly, as shown in Figure 1, rechargeable nonaqueous electrolytic battery 1 of the present invention is anodal 3 with the configuration of the sequential cascade of dividing plate-negative pole-dividing plate-positive pole across dividing plate 7, negative pole 5, is that the mode of inboard is reeled and constituted electrode plate groups with anodal 3, is inserted in the battery can 25.Anodal then 3 are connected to positive terminal 29 by positive wire 27, and negative pole 5 is connected to battery can 25 by negative wire 31, being taken out to the outside in the electric energy mode at the rechargeable nonaqueous electrolytic battery 1 inner chemical energy that produces.Then, after being filled in the battery can 25 in the mode of coated electrode plate group non-aqueous electrolyte 8, will be 29 that constitute by the positive terminal on circular cover and top thereof, seal body 33 that its inside is built-in with relief valve mechanism, be installed on the upper end (peristome) of battery can 25 by the ring-type insulation spacer, can make rechargeable nonaqueous electrolytic battery 1 of the present invention.
(the 7. effect of rechargeable nonaqueous electrolytic battery of the present invention)
Rechargeable nonaqueous electrolytic battery of the present invention is because use comprises the nano size particles of the high Si of the Capacity Ratio carbon of per unit volume as negative electrode active material, therefore specific capacity is big mutually with in the past lithium rechargeable battery, and nano size particles is difficult for micronizing, so cycle characteristics is good.
In addition, form under the situation of negative pole at the negative electrode active material that uses such nano-scale, with rubbing method, also can by in electrolyte, comprise have unsaturated bond can reductive polymerization organic substance, and form stable epithelium effectively on the negative electrode active material layer surface, make negative electrode active material stable, the decomposition of electrolyte is suppressed, and cycle characteristics improves.
Embodiment
Below, specify the present invention with embodiment and comparative example.
[embodiment 1]
(nano size particles)
Use the device of Fig. 8, with mol ratio Si: Fe=23: 2 mode is mixed Si powder and iron powder, the mixed-powder of drying as material powder, is supplied to carrier gas in the plasma of the Ar gas that produces in reative cell continuously, makes the nano size particles of silicon and iron thus.
In detail, make with method described as follows.After carrying out exhaust in to reative cell, import Ar gas to becoming atmospheric pressure with vacuum pump.Repeat 3 these exhausts and Ar gas and import, the residual air in the reaction vessel is discharged.Thereafter, the flow with 13L/min in reaction vessel imports Ar gas as plasma gas, and high frequency coil is imposed alternating voltage, utilizes electromagnetic field of high frequency (frequency is 4MHz) to produce high-frequency plasma.The pole plate electric power of this moment is made as 20kW.The carrier gas that is used for the base feed powder has been used the Ar gas of flow velocity as 1.0L/min.Reclaim resulting attritive powder with filter.
(evaluation of the formation of nano size particles)
About the crystallinity of nano size particles, use Rigaku corporate system RINT-UltimaIII to carry out XRD and resolve.The XRD diffracting spectrum that shows the nano size particles of embodiment 1 among Figure 11.Embodiment 1 resulting nano size particles is by Si and FeSi as can be known 2This 2 composition constitutes.In addition, as can be known Fe all with silicide FeSi 2Form exists, and exists hardly as the Fe of element monomer (valence mumber is 0).
Use scanning transmission electron microscope (NEC system, JEM 3100FEF) to carry out the observation of the shape of particle of nano size particles.Figure 12 (a) be the nano size particles of embodiment 1 BF-STEM (Bright-Field Scanning Transmission Electron Microscopy, light field scanning transmission electron microscope) as.Observing hemispheric particle is roughly spherical particle about about 80～100nm by interface in particle diameter, and in same particle, the denseer place of color is made of the ferrosilite of iron content, and the more shallow place of color is made of silicon.In addition, be formed with the oxide-film that unbodied thickness is the silicon of 2～4nm as can be known on the nano size particles surface.Figure 12 (b) is for passing through HAADF-STEM (High-Angle-Annular-Dark-Field-Scanning Transmission-Electron-Microscopy: high angle scattering details in a play not acted out on stage, but told through dialogues-scanning transmission electron microscope method) resulting STEM photo.Among the HAADF-STEM, in same particle the more shallow place of color by ferrosilite constitute, the denseer place of color is made of silicon.
The observation of the shape of particle of nano size particles and composition analysis use scanning transmission electron microscope (NEC system, JEM 3100FEF), utilize the observation of shape of particle of HAADF-STEM and EDS (Energy Dispersive Spectroscopy: the energy dispersion type x-ray analysis) analyze and carry out.Figure 13 (a) is the HAADF-STEM picture of nano size particles, and Figure 13 (b) is the EDS collection of illustrative plates at the silicon atom of same observation place, and Figure 13 (c) is the EDS collection of illustrative plates at the iron atom of same observation place.
According to Figure 13 (a), observe particle diameter and be the nano size particles about about 50～150nm, each nano size particles is respectively done for oneself roughly spherical.By Figure 13 (b) as can be known, silicon atom is present in the integral body of nano size particles, and by Figure 13 (c) as can be known, observed bright place detects a large amount of iron atoms among Figure 13 (a).By above thing card as can be known, nano size particles has by the 2nd engaging to the 1st structure that forms mutually that is formed by silicon that the silicon and the compound of iron form.
Figure 14 (a)～(c) has carried out the observation and the composition analysis of shape of particle of other nano size particles of embodiment 1 similarly.Figure 14 also with Figure 13 similarly, have as can be known by the 2nd engaging that the silicon and the compound of iron form to the 1st structure that forms mutually that forms by silicon.
Forming process to resulting nano size particles is studied.Figure 15 is the binary system state diagram of Si and Fe.Because with the mol ratio is Si: Fe=23: 2 mode has been mixed Si powder and iron powder, thereby the mol ratio Si/ of material powder (Fe+Si)=0.92.Thick line among Figure 15 is for showing the line of mol ratio Si/ (Fe+Si)=0.92.Because the plasma that high frequency coil generated is equivalent to 10,000 K, therefore far exceeds the temperature range of state diagram, thereby can obtain iron atom and the mixed uniformly plasma of silicon atom.If plasma cooling, then by plasma to gas, by the gas spherical drop of in the process that liquid changes, growing, if be cooled to about 1470K then Fe 3Si 7All separate out with Si.Thereafter, if be cooled to about 1220K, Fe then 3Si 7Phase transformation turns to FeSi 2With Si.Therefore, if the cooling of the plasma of silicon and iron then can form FeSi 2With the nano size particles of Si by interface.Because the compatibility of Si and Fe is low, thereby Si takes two particles to engage the shape that forms with Fe, with the minimizing area that contacts with each other.
The average grain diameter of resulting nano size particles is 100nm.
(evaluation of powder conductance)
In order to estimate the electronic conductivity of powder state, use the powder resistance mensuration MCP-PD51 of the system type of Mitsubishi Chemical's system to carry out the evaluation of powder conductance.The resistance value of conductance according to any pressure compression samples powder the time asked for.The data of aftermentioned table 1 are for 63.7Mpa compression samples powder and the value when measuring.
(evaluation of the cycle characteristics of rechargeable nonaqueous electrolytic battery)
(i) preparation of negative pole slurries
Si that use obtains hereinbefore and the nano size particles of Fe are as negative electrode active material, drop into acetylene black (Deuki Kagaku Kogyo Co., Ltd's system, powdery product) as electric conducting material to blender, further mix emulsion (Japanese ZEON (strain) system, BM-400B) then as styrene butadiene rubbers (SBR) 40wt% of binding agent, as sodium carboxymethylcellulose (Daicel chemical industry (strain) system, #2200) the 1wt% solution of the thickener that is used to regulate slurry viscosity, make slurries.For the cooperation of slurries, negative electrode active material is that 64 weight %, electric conducting material are that 16 weight %, binding material (solid constituent conversion) 5 weight %, thickening material (solid constituent conversion) are 15 weight %.
The (ii) making of negative pole
Use the scraper of automatic apparatus for coating, the thickness of prepared slurries with 15 μ m is coated on the collector body electrolytic copper foil that thickness is 10 μ m (Furukawa electrical industry (strain) system, NC-WS), drying is 10 minutes under 70 ℃, makes negative pole A.
(iii) estimate
Test electrode uses negative pole A, uses lithium, dividing plate to use the microporous barrier of polyolefin system, electrolyte use comprising the LiPF of 1.3mol/L to electrode and reference electrode 6Ethylene carbonate (EC), methyl ethyl carbonate (EMC), with the mixed solution of dimethyl carbonate (DMC) in added the electrolyte of the vinylene carbonate (VC) of 1 weight %, constitute evaluation electricity pool, the research charge-discharge characteristic.
In addition, for the evaluation of charge-discharge characteristic, measure first discharge capacity and 50 times the charge/discharge of circulating after discharge capacity, ask for discharge capacity behind the charge/discharge of circulation 50 times with percentage with respect to the ratio of first discharge capacity, with it as the capacity sustainment rate.Discharge capacity is that benchmark is calculated with the weight of following active material Si (being Si and Sn under the situation that also comprises Sn), described active material Si be removed form silicide etc. and can not embed/silicon of removal lithium embedded and tin, to the effective active material Si of embedding/removal lithium embedded.At first, under 25 ℃ environment,, carry out constant-current charge, carry out constant-voltage charge to current value and be reduced to 0.05C to voltage to 0.02V with the electric current of 0.1C.Then,, carry out constant-current discharge, measure 0.1C initial stage discharge capacity to voltage to 1.5V with the electric current of 0.1C.Need to prove that 1C is can be to be full of the current value of electricity in 1 hour.Then, repeat above-mentioned charge and discharge cycles 50 times.
[embodiment 2]
Use the device of Fig. 8, be Si: Fe=38 with the mol ratio: 1 mode is mixed Si powder and iron powder, and as material powder, with method similarly to Example 1, making average grain diameter is the nano size particles of 100nm with the mixed-powder of drying.Then, use this nano size particles, make negative pole B, make up evaluation electricity pool, the research charge-discharge characteristic with method similarly to Example 1 as negative electrode active material.
The XRD diffracting spectrum that shows the nano size particles of embodiment 2 among Figure 16.Embodiment 2 is by Si and FeSi as can be known 22 compositions constitute.In addition, as can be known Fe all with silicide FeSi 2Form exists, and the Fe of element monomer exists hardly.In addition, if compare with Fig. 9, compare with the nano size particles of embodiment 1, the ratio of Fe is few, is derived from FeSi 2The peak can only confirm the vestige degree.
To be shown in Figure 17 based on the observed result of STEM.According to Figure 17 (a), observe a large amount of diameters and be the roughly spherical particle about 50～150nm.In underlapped particle, dark part is considered to ferrosilite, and light-colored part is considered to silicon.Observe in addition, arranging the atomic rule of silicon part, as can be known, the silicon that belongs to the 1st phase is crystalline.In addition, by Figure 17 (b) as can be known,, partly be covered with the unformed layer of thickness, partly be covered with the unformed layer of thickness for about 2nm in ferrosilite for about 1nm in silicon on the surface of nano size particles.In addition, the comparison of the STEM photo by Figure 12 and Figure 17 can be confirmed Si and FeSi 2Relative size, the FeSi of the nano size particles of embodiment 2 as can be known 2FeSi than the nano size particles of embodiment 1 2Little.
To the results are shown in Figure 18, Figure 19 based on what the observation of the shape of particle of HAADF-STEM and EDS analyzed.According to Figure 18 (a), observe particle diameter and be the nano size particles about about 150～250nm, it is roughly spherical that each nano size particles is respectively.By Figure 18 (b) as can be known, silicon atom is present in the integral body of nano size particles, and by Figure 18 (c) as can be known, observed bright place detects a large amount of iron atoms among Figure 18 (a).By Figure 18 (d) as can be known, be considered to the oxygen atom trace that oxidation produces and be distributed in nano size particles integral body.
Similarly, according to Figure 19 (a), observe the roughly spherical nano size particles of particle diameter for about 250nm, by Figure 19 (b) as can be known, silicon atom is present in the integral body of nano size particles, and by Figure 19 (c) as can be known, observed bright place detects a large amount of iron atoms among Figure 19 (a).By Figure 19 (d) as can be known, be considered to the oxygen atom trace that oxidation produces and be distributed in nano size particles integral body.By above thing card as can be known, nano size particles has by the 2nd engaging to the 1st structure that forms mutually that is formed by silicon that the silicon and the compound of iron form.
[embodiment 3]
Use the device of Fig. 8, be Si: Ni=12 with the mol ratio: 1 mode is mixed Si powder and iron powder, and as material powder, with method similarly to Example 1, making average grain diameter is the nano size particles of 100nm with the mixed-powder of drying.Then, use this nano size particles, make negative pole C, make up evaluation electricity pool, the research charge-discharge characteristic with method similarly to Example 1 as negative electrode active material.
The XRD diffracting spectrum that shows the nano size particles of embodiment 3 among Figure 20.Embodiment 3 is by Si and NiSi as can be known 2This 2 composition constitutes.In addition, as can be known Ni all with silicide NiSi 2Form exists, and the Ni of element monomer (valence mumber is 0) exists hardly.Si and NiSi as can be known 2The angle of diffraction 2 θ unanimities, and face is at interval almost consistent.
Figure 21 (a) is the BF-STEM picture, and Figure 21 (b) is the HAADF-STEM picture of the same visual field.According to Figure 21, observe particle diameter and be the nano size particles about about 75～150nm, each nano size particles has the shape that roughly hemispheric other particle forms in each roughly spherical macroparticle by interface.
Figure 22 is the high-resolution TEM picture of the nano size particles of embodiment 3.Observe crystal lattice pattern among Figure 22 (a)～(c), silicon is roughly consistent with the lattice fringe of silicide phase, and silicide becomes polyhedron-shaped as can be known.In addition, silicon and silicide border mutually linearly, curve or stepped.In addition, the surface coverage of nano size particles the unformed layer of thickness for the silicon of about 2nm as can be known.
The result that the HAADF-STEM picture of the nano size particles of demonstration embodiment 3 and EDS analyze among Figure 23.According to Figure 23 (a), observe particle diameter and be the nano size particles about about 75～150nm.By Figure 23 (b) as can be known, silicon atom is present in the integral body of nano size particles, and by Figure 23 (c) as can be known, observed bright place detects a large amount of nickle atoms among Figure 23 (a).By above thing card as can be known, nano size particles has by the 2nd engaging to the 1st structure that forms mutually that is formed by silicon that the silicon and the compound of nickel form.In addition, by Figure 23 (d) as can be known, be considered to the oxygen atom trace that oxidation produces and be distributed in nano size particles integral body.
[embodiment 4]
Use the device of Fig. 8, so that mol ratio is Si: Fe: Sn=21: 1: 1 mode is mixed Si powder and iron powder, and as material powder, with method similarly to Example 1, making average grain diameter is the nano size particles of 100nm with the mixed-powder of drying.Then, use this nano size particles, make negative pole D, construction evaluation electricity pool, research charge-discharge characteristic with method similarly to Example 1 as negative electrode active material.
Figure 24 is X-ray diffraction (XRD) collection of illustrative plates of the nano size particles of embodiment 4.The nano size particles of embodiment 4 has Si, Sn and FeSi as can be known 2
The STEM photo of the nano size particles of embodiment 4 is shown in Figure 25 (a)～(b).The outer surface of observing particle diameter and being about about 50～150nm is the nano size particles of dome shape roughly.Among Figure 25 (a), dark part is considered to Sn, and place of light color is considered to Si.
The STEM photo of the nano size particles of embodiment 4 is shown in Figure 26 (a)～(b).The outer surface of observing particle diameter and being about about 50～150nm is the nano size particles of dome shape roughly.Bright areas is considered to mainly be made of Sn, and dark areas is considered to mainly be made of Si.
According to Figure 27 (a), observe the nano size particles that particle diameter is about 100～150nm, by Figure 27 (b) as can be known, observed dark place detects a large amount of silicon atoms among Figure 27 (a).By Figure 27 (c) as can be known, observed little bright place detects a large amount of iron atoms among Figure 27 (a).By Figure 27 (d) as can be known, observed bright place detects a large amount of tin atoms among Figure 27 (a).By Figure 27 (e) as can be known, be considered to the oxygen atom that oxidation produces and be distributed in nano size particles integral body.
Figure 28 is the figure that further shows the EDS analysis result.Figure 28 (a) is the EDS collection of illustrative plates of Fe and Sn and the figure that they are stacked, and Figure 28 (b) is at the HAADF-STEM of the same visual field figure.According to Figure 28 (a), the detection site of Sn and Fe overlapping few.XRD is also unconfirmed to the peak that is derived from the Sn-Fe alloy in resolving, and does not therefore form the Sn-Fe alloy in this nano size particles.In addition, Si and Sn be not owing to form alloy, so Sn exists with monomer.
Figure 29 is for showing the figure of the EDS analysis result at the 1st～the 3rd place in the nano size particles.The 1st place at Figure 29 (b) mainly observes Si, observes micro-Sn.The 2nd place at Figure 29 (c) observes Si and Sn.The 3rd place at Figure 29 (d) mainly observes Si and Fe, observes micro-Sn.In addition, when observing, observe the Cu background that is derived from the TEM mesh that keeps sample widely.
[comparative example 1]
As negative electrode active material, use average grain diameter to replace nano size particles as the silicon nano (Hefei Kai ' er NanoTech system) of 100nm, make negative pole E with method similarly to Example 1 then, and the construction evaluation electricity pool, the research charge-discharge characteristic.
[comparative example 2]
Test electrode uses the negative pole A that makes similarly to Example 1, and electrode and reference electrode are used lithium, and dividing plate uses the microporous barrier of polyolefin system, and electrolyte uses the LiPF that comprises 1.3mol/L 6Ethylene carbonate (EC), methyl ethyl carbonate (EMC), and the electrolyte of the mixed solution of dimethyl carbonate (DMC), constitute evaluation electricity pool, the research charge-discharge characteristic.That is, do not add vinylene carbonate (VC) in the electrolyte.
[comparative example 3]
Test electrode uses the negative pole B that makes similarly to Example 2, then with comparative example 2 construction evaluation electricity pools similarly, research charge-discharge characteristic.
[comparative example 4]
Test electrode uses the negative pole C that makes similarly to Example 3, then with comparative example 2 construction evaluation electricity pools similarly, research charge-discharge characteristic.
[comparative example 5]
Test electrode uses the negative pole D that makes similarly to Example 4, then with comparative example 2 construction evaluation electricity pools similarly, and the research charge-discharge characteristic.
[comparative example 6]
Test electrode uses the negative pole E that similarly makes with comparative example 1, then with comparative example 2 construction evaluation electricity pools similarly, and the research charge-discharge characteristic.
(evaluation of nano size particles)
To be nano size particles to the Si of embodiment 1～4, comparative example 1～6 with the method shown in the embodiment 1, the powder conductance under the condition of 63.7Mpa lower compression powder particle, measured, be shown in table 1.
The powder conductance that demonstrates embodiment 1～4, comparative example 2～5 is 4 * 10 -8More than [S/cm], the powder conductance of comparative example 1,6 is less than 4 * 10 -8[S/cm].In addition, comparative example 1,6 is 1 * 10 less than determination limit -8[S/cm].If powder conductance height then can reduce the cooperation of conductive auxiliary agent, can improve the capacity of the per unit volume of electrode, and favourable aspect the high magnification characteristic.
[table 1]
Figure BPA00001718570300291
The discharge capacity and the capacity sustainment rate of embodiment 1～4, comparative example 1～6 are shown in table 2.In addition, show embodiment 1～4, the period of comparative example 1～6 and the relation of discharge capacity sustainment rate among Figure 30.
[table 2]
By table 2 and Figure 30 obviously as can be known, when comparing embodiment 1～embodiment 4 and comparative example 2～comparative example 5, by in electrolyte, adding VC, unexpectedly improved more than 2 times at the capacity sustainment rate of circulation after 50 times, the reduction of the capacity of the rechargeable nonaqueous electrolytic battery of embodiment 1～embodiment 4 is inhibited as can be known, and cycle characteristics is good.
And then, also be conceived to the result of comparative example 1 and comparative example 6, rechargeable nonaqueous electrolytic battery of the present invention has as can be known obtained the preferable inhibition effect that the aforesaid capacity that obtains by interpolation VC in electrolyte reduces, but the nano size particles that is to use Si not only can not get effect fully as the rechargeable nonaqueous electrolytic battery of negative electrode active material, and charge-discharge characteristic is reduced.
In the present embodiment, as negative electrode active material, though used Fe and Ni as form with compound with Si the 2nd mutually element M, use Sn as the elements A that forms the 3rd phase, can be used in negative electrode active material of the present invention and be not limited to this.So long as comprise the 1st phase that constitutes by Si, the compound MSi that reaches element M and Si at least XThe nano size particles of the 2nd phase of (1＜X≤3) gets final product, and can infer, for example uses Ti or Co also can obtain same result except Fe and Ni.
In the present embodiment,, can be used in and of the present inventionly in molecule, have unsaturated bond and organic substance that can reductive polymerization is not limited to this though use vinylene carbonate as in molecule, having unsaturated bond and organic substance that can reductive polymerization.As long as at the charging potential reductive polymerization of negative pole and can form stable overlay film on the negative electrode active material surface, can infer, for example use vinylethylene carbonate also can obtain result with the present embodiment same tendency.
Though more than preferred embodiment describe of the present invention, the present invention is not limited to these examples.Should be understood that so long as those skilled in the art in the then disclosed in this application technological thought category, can expect various modifications or revise example that this is conspicuous, and these are subordinated to also in the technical scope of the present invention certainly.
Symbol description
Figure BPA00001718570300301
Figure BPA00001718570300311

Claims (13)

1. rechargeable nonaqueous electrolytic battery, it is characterized in that, its have can embed and the positive pole of removal lithium embedded ion, can embed and the negative pole of removal lithium embedded ion and be disposed at described positive pole and described negative pole between dividing plate, and, described positive pole, described negative pole and described dividing plate are arranged in the nonaqueous electrolytic solution with lithium-ion-conducting, wherein
The negative electrode active material of described negative pole comprises the 1st particle that contains element X and the 2nd particle that contains element M,
Described element X is at least a kind of element that is selected from the group of being made up of Si, Sn, Al, Pb, Sb, Bi, Ge, In, Zn,
Described element M is at least a kind of element that is selected from the group of being made up of the transition metal of the 4th～11 family,
Described the 1st particle is made of monomer or the solid solution of described element X,
Described the 2nd particle is made of the monomer or the compound of described element M,
And described electrolyte contains and has unsaturated bond and organic substance that can reductive polymerization in the molecule.
2. rechargeable nonaqueous electrolytic battery according to claim 1, wherein, the average grain diameter of described the 1st particle is 2nm～500nm, the average grain diameter of described the 2nd particle is 2nm～10 μ m.
3. rechargeable nonaqueous electrolytic battery according to claim 1, wherein, in the described negative pole, the surface of described the 2nd particle of the surface lies of described the 1st particle is in 1 μ m.
4. non-hydrolysis electrolyte secondary battery, it is characterized in that, its have can embed and the positive pole of removal lithium embedded ion, can embed and the negative pole of removal lithium embedded ion and be disposed at described positive pole and described negative pole between dividing plate, and, described positive pole, described negative pole and described dividing plate are arranged in the nonaqueous electrolytic solution with lithium-ion-conducting, wherein
The negative electrode active material of described negative pole is made of the nano size particles of containing element X and element M,
Described element X is the a kind of element that is selected from the group of being made up of Si, Sn, Al, Pb, Sb, Bi, Ge, In, Zn,
Described element M is at least a kind of element that is selected from the group of being made up of the transition metal of the 4th～11 family,
Described nano size particles has the 1st phase as the monomer of described element X or solid solution at least, and as the 2nd phase of the monomer or the compound of described element M,
And described electrolyte contains and has unsaturated bond and organic substance that can reductive polymerization in the molecule.
5. rechargeable nonaqueous electrolytic battery according to claim 4, wherein, described nano size particles the described the 1st with the described the 2nd the two is exposed to outer surface mutually, and by interface, the outer surface of described the 1st phase is dome shape roughly.
6. rechargeable nonaqueous electrolytic battery according to claim 4, wherein, the average grain diameter of described nano size particles is 2nm～500nm.
7. rechargeable nonaqueous electrolytic battery according to claim 4, wherein, the further containing element M ' of described nano size particles, it is at least a kind of element that is selected from the group of forming by Cu, Fe, Co, Ni, Ca, Sc, Ti, V, Cr, Mn, Sr, Y, Zr, Nb, Mo, Tc, Ru, Rh, Ba, with lanthanide series, Hf, Ta, W, Re, Os, Ir except Ce and the Pm
Described element M ' be and constitute the described the 2nd mutually the diverse element of described element M;
And further have as described element M ' monomer or another the 2nd phase of compound.
8. rechargeable nonaqueous electrolytic battery according to claim 4, the further containing element X ' of wherein said nano size particles, it is at least a kind of element that is selected from the group of being made up of Si, Sn, Al, Pb, Sb, Bi, Ge, In, Zn,
And further has the 3rd phase as monomer or the solid solution of described element X '.
9. non-hydrolysis electrolyte secondary battery according to claim 8, wherein, the described the 3rd reaches the described the 2nd at least one joint in mutually mutually by interface and the described the 1st.
10. non-hydrolysis electrolyte secondary battery according to claim 1, wherein, described the 1st particle is the described nano size particles of claim 4.
11. according to claim 1 or 4 described non-hydrolysis electrolyte secondary batteries, wherein, having unsaturated bond and organic substance that can reductive polymerization in the described molecule is at least a kind that is selected from the group of being made up of fluorinated ethylene carbonate, vinylene carbonate and derivative thereof and vinylethylene carbonate.
12. non-hydrolysis electrolyte secondary battery according to claim 11, wherein, having unsaturated bond and organic addition that can reductive polymerization in the described molecule is the 0.1 weight %～10 weight % of electrolyte weight.
13. according to claim 1 or 4 described non-hydrolysis electrolyte secondary batteries, wherein, described negative pole is coated collector body and dry formation by the coating fluid that will comprise negative electrode active material, electric conducting material and binding material at least.
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