CN108539198A - Secondary battery anode active compound coating solvent, the anode active material slurry comprising it and the secondary cell that is produced from it - Google Patents
Secondary battery anode active compound coating solvent, the anode active material slurry comprising it and the secondary cell that is produced from it Download PDFInfo
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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
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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- 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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- 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
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Abstract
A kind of anode active material slurry the present invention relates to secondary battery anode active compound coating solvent, comprising it and the secondary cell that is produced from it.Specifically, according to the present invention, positive active material can be made very stably to disperse, the anode active material slurry loaded with high-content is provided, the positive electrode active material layer that load deviation is substantially reduced can be not only formed using it, but also the secondary cell with the capacity characteristic and life characteristic significantly improved can be provided.
Description
Technical field
The present invention relates to secondary battery anode active compound coating solvent, comprising its anode active material slurry and
The secondary cell being produced from it.
Background technology
With electronic industry, including mobile communication various information communication etc. communications industries high speed development, cater to
The light and shortization requirement of electronic equipment, such as laptop, net book, tablet computer, mobile phone, smart mobile phone, PDA, number
Code camera, the sub- product of Portable power of video camera etc. and communication terminal device are just widely available, therefore, for as these
The exploitation of the battery of device drives power supply, also increasingly pays close attention to.
In addition, with the electric vehicle of such as hydrogen cell automobile or hybrid vehicle, fuel cell car etc
Exploitation, huge pass has been suffered to the development set of the battery with high-performance, large capacity, high density and high power, high stability
The exploitation of note, the battery with fast charging and discharging characteristic also becomes unprecedented hot spot.
According to this trend, now with high-energy density and voltage, have extended cycle life, lithium that self-discharge rate is low it is secondary
Battery just in commercialization and is widely used, and in order to make said effect maximize, actively carries out grinding lithium secondary battery
Study carefully.
Secondary cell is with positive (positive electrode), cathode (negative electrode), seperation film
(separator) and electrolyte (electrolyte) is basic inscape.Above-mentioned anode and cathode are as generation oxygen
The electrode for changing transformation and the storages of energy such as reduction, is respectively provided with positive and negative current potential.Above-mentioned seperation film is located at positive electrode and negative electrode
Between, electric insulation is kept, the movable passageway of charge is provided.In addition, above-mentioned electrolyte plays the role of the medium of charge transfer.
For the lithium secondary battery as one of secondary cell example, battery performance (such as capacity etc.) is by being made
The biggest impact of positive active material.In order to improve the performance of this lithium secondary battery, positive active material should be can
While with high numerical value load appropriate, thick layer uniformly, stable is formed on the current collector.In order to solve this project, answer
Easily adjust solid component content, the viscosity etc. of above-mentioned anode active material slurry.
At this point, above-mentioned lithium secondary battery anode can by will include positive active material positive electrode active material chylema
For material coated on positive electrode collector and dry and manufacture, above-mentioned anode active material slurry can be in positive active material
The mixture with mobility for adding adhesive and organic solvent and mixing.
Common positive active material is by adding a large amount of organic solvent (for example, n-methyl-2-pyrrolidone (NMP)
Deng) and suitably adjust viscosity so that the large specific surface area that particle size is small, carbon applies is including its positive active material
There is lower solid component concentration (solid constituent 45% is horizontal), to solve the above subject in slurry.But a large amount of
In the case of using organic solvent, though after the drying if undried part can occur, cannot achieve the load of high-content
(high-loading), the processes speed such as rate of drying increases, and induces the problem of productivity declines.In addition, just having low solid
For the anode active material slurry of constituent concentration, since dispersion stabilization reduces, when forming positive electrode active material layer, tool
It is possible that the problem of causing layer thickness and load deviation.Especially because the harmfulness of above-mentioned organic solvent, has not environmentally friendly enough
The problem of.
Under background as described above, the present inventor is during the research for deeply carrying out being intended to improve the above problem
Confirm, using the coating solvent for including N- ethyl-formamides (N-ethylformamide), can not only improve packet tremendously
The dispersibility of slurry containing positive active material, moreover, positive electrode active material layer is stably formed with uniform thickness, so as to
With anode of the offer with the capacity characteristic and life characteristic improved and comprising its secondary cell, so as to complete this hair
It is bright.
Existing technical literature
Patent document
Patent document 1：KR 10-0436708 B1
Patent document 2：KR 10-1764470 B1
Invention content
It is an object of the present invention to provide one kind having low viscosity under higher-solid concentration, while to anode
In terms of the dispersion stabilization of active material outstanding secondary battery anode active compound coating solvent and comprising it just
Pole active material slurry.
Another object of the present invention is to provide a kind of comprising the positive active material formed by above-mentioned anode active material slurry
The anode of layer and the secondary cell including it.
In order to solve the above problems, the present invention provides a kind of secondary battery anode active compound coating solvent, wherein
Including N- ethyl-formamides.
In addition, a kind of anode active material slurry of present invention offer is comprising positive active material, adhesive and N-
Ethyl-formamide.
For the anode active material slurry of one embodiment of the invention, above-mentioned positive active material can be used as follows
Chemical formula 1 indicates.
[chemical formula 1]
Li1+x[NiaCobMnc]O2
[in above-mentioned chemical formula 1, -0.5≤x≤0.6,0≤a, b, c≤1, x+a+b+c=1.]
For the anode active material slurry of one embodiment of the invention, above-mentioned adhesive can be selected from fluorine system and bond
Agent and elastomeric adhesive.
For the anode active material slurry of one embodiment of the invention, it is with anode active material slurry total weight
The solid component content of benchmark, above-mentioned anode active material slurry can be 30~80 weight %.
For the anode active material slurry of one embodiment of the invention, with the total solid of anode active material slurry
On the basis of component content, above-mentioned positive active material can be 55~99 weight %.
For the anode active material slurry of one embodiment of the invention, above-mentioned anode active material slurry can be also
Including conductive material.
For the anode active material slurry of one embodiment of the invention, above-mentioned conductive material can be selected from carbon system object
Matter.
In addition, the present invention provides a kind of anode, wherein include being lived by the anode that above-mentioned anode active material slurry is formed
Property material layer.
In addition, the present invention may include the seperation film between above-mentioned anode, cathode and above-mentioned positive and above-mentioned cathode, and
Above-mentioned anode can form positive electrode active material layer in the one side of positive electrode collector with 10~100 μm of thickness.
For the secondary cell of one embodiment of the invention, the initial discharge capacity of above-mentioned secondary cell can be
200mAh/g or more, 50 times cycle in capacity maintenance rate can be 90% or more.
For the secondary cell of one embodiment of the invention, the C-rate of above-mentioned secondary cell indicated with following formula 1
Efficiency can be 90% or more.
[formula 1]
C-rate (%)=[(2C discharge capacities)/(0.1C discharge capacities)] × 100
According to the present invention, there are low viscosity characteristics under higher-solid concentration, can easily embody to just
The high load content of pole active material, when being mixed with positive active material, dispersibility is remarkable, even if being used for a long time or protecting
Guan Zhong can also keep highly stable phase.
In addition, according to the present invention, without using the high organic solvent (for example, NMP etc.) of previous environment harmfulness, thus can
Positive active material and the anode comprising it with environmentally friendly are provided.
In addition, according to the present invention it is possible to providing the secondary cell with the capacity characteristic and life characteristic improved.Especially
It is that high initial discharge capacity is not only, and even if at 50 times after cycle, still show high electric discharge and hold according to the present invention
Amount, shows the capacity maintenance rate significantly improved.
Specific implementation mode
If with reference to latter embodiments, advantages and features of the invention and reaches its method and will define.But
It is that the present invention is not limited to embodiments disclosed below, can be embodied with mutually different variform, but, this implementation
Example is completely to inform the scope of invention to those skilled in the art in order to keep disclosure of the invention more complete and provide, this
Invention is only defined by claims.Just the secondary battery anode active compound of the present invention coats with solvent, includes it below
Anode active material slurry and the secondary cell that is produced from it be described in detail.
The present invention provides the secondary battery anode active compound coating solvent for including N- ethyl-formamides.The present invention's
Coating solvent is characterized in that, when being mixed with positive active material, shows the dispersibility improved.Although can not know
Accurate reason, it is contemplated that being caused by the interaction of the N- ethyl-formamides and positive active material of the present invention.Judge
Think that above-mentioned interaction is the physics due to shared and non-shared interaction of such as hydrogen bond, hydrophobic interaction
Entanglement etc. is interim or has an impact for a long time.
This phenomenon be comprising surprising synergistic effect caused by N- ethyl-formamides, with above-mentioned N- ethyls
Benzamide type is completely unconfirmed in the Carbox amide (for example, formamide, N-METHYLFORMAMIDE etc.) like Structural Characteristics
It arrives, there is huge meaning in this regard.
In addition, the secondary battery anode active compound coating of the present invention does not use such as usually used N- first with solvent
The harmful organic solvent of base -2-Pyrrolidone (NMP) etc., so as to provide positive electrode active material layer in more environmentally friendly method
And include its electrode.
In addition, the present invention provides the anode active material slurry for including N- ethyl-formamides.
Specifically, above-mentioned anode active material slurry can include positive active material, adhesive and N- ethyl formyls
Amine etc..
The anode active material slurry of one embodiment of the invention can include to be lived with the anode that following chemical formula 1 indicates
Property substance.
[chemical formula 1]
Li1+x[NiaCobMnc]O2
[in above-mentioned chemical formula 1, -0.5≤x≤0.6,0≤a, b, c≤1, x+a+b+c=1.]
The anode active material slurry of one embodiment of the invention not only can effectively inhibit above-mentioned positive active material
Capacity reduces, and can prevent that the problem of gas etc. leads to cell expansion occurs due to remaining lithium content and rising, from this side
Can include to be selected from LiCoO for face2、LiNiO2And LiMnO2At least one of Deng.
In addition, the anode active material slurry of one embodiment of the invention can also include additional positive active material.
As an example, additional positive active material can be selected from LiFePO4、 LiFeMnPO4、LiFeMgPO4、
LiFeNiPO4、LiFeAlPO4And LiFeCoNiMnPO4One or more of Deng, but it is not limited to this.
For the anode active material slurry of one embodiment of the invention, above-mentioned adhesive, which is used as, to be contributed in anode
The combination for the metal oxide-coated layer that active material surface is formed or contribute to the combination of the conductive material etc. of addition at
Point, as long as substance commonly used in the art, then be not limited, but specifically, can be selected from fluorine system adhesive and
One or more of elastomeric adhesive etc..
As an example, above-mentioned fluorine system adhesive can be Kynoar (PVDF), biasfluoroethylene-hexafluoropropylene
Copolymer (PVDF-co-HEP), chlorotrifluoroethylene (CFTF) and polytetrafluoroethylene (PTFE) (PTFE) etc..
As an example, above-mentioned elastomeric adhesive can be styrene butadiene ribber (SBR), butadiene rubber
(BR), nitrile rubber (NBR) and isoprene rubber (IR) etc..
In addition, for the anode active material slurry of one embodiment of the invention, above-mentioned adhesive can also include choosing
From acrylic adhesives such as polyacrylonitrile, polymethyl methacrylate, polyacrylic acid；Polyvinyl alcohol, polyvinylpyrrolidine
Ketone, polyethylene, polypropylene, olefin-based adhesive；And carboxymethyl cellulose, hydroxypropyl methyl cellulose, regenerated cellulose etc.
One or more of cellulose-based adhesive.
The anode active material slurry of one embodiment of the invention on the basis of anode active material slurry total weight, Gu
Body component content can be 30~80 weight %.At this point, surplus is N- ethyl-formamides.
As described above, N- ethyl-formamides are used as dispersant by the anode active material slurry of the present invention, that is, it is used as anode
Active material coating solvent, thus even if under higher-solid content, low viscosity can not only be embodied, and significantly carry
Its high dispersion stabilization.
The anode active material slurry of one embodiment of the invention on the basis of anode active material slurry total weight, Gu
Body component content is specifically as follows 30~70 weight %, can be 40~60 weight % more specifically.
In addition, the anode active material slurry of one embodiment of the invention can have 5000~30000g/cms (
At 23 DEG C, using it is rich Le fly in circles transition viscosimeter, be measured with 20rpm) viscosity, specifically, can have 8000~
The viscosity of 30000g/cms more specifically can be with the viscosity of 10000~25000g/cms.Above-mentioned viscosity model
Enclose 30~60% horizontal low viscosities when being equivalent to common NMP etc. as solvent.
As an example, the anode active material slurry (positive electrode active material with 45 weight % solid component contents
Matter：Adhesive=98:2(wt:It wt)) can be with the viscosity of 11000~20000g/cms.At this point, above-mentioned positive electrode active material
The rate of change in viscosity (viscosity/initial viscosity × 100, high temperature keeping are 45 DEG C of conditions after high temperature keeping in 1 day) of chylema material has 1
~5% range.
As an example, the anode active material slurry positive active material with 50 weight % solid component contents：
Adhesive=98:2(wt:It wt)) can be with the viscosity of 15000~23000g/cms.At this point, above-mentioned positive active material
The rate of change in viscosity (viscosity/initial viscosity × 100 after high temperature keeping in 1 day) of slurry has 1~5% range.
For the anode active material slurry of one embodiment of the invention, above-mentioned positive active material is with above-mentioned anode
Can include 55~99 weight % on the basis of the total solid content content of active material slurry, specifically, can include 60
More specifically~99 weight % can include 65~99 weight %.At this point, surplus can be adhesive.
Even if the anode active material slurry of one embodiment of the invention under higher-solid content as described above,
Also form stable dispersed phase, even thus relatively low viscosity, also without physical property change (example, viscosity) worry.As above
It is described, it can be kept if even if forming the above-mentioned anode active material slurry of stable dispersed phase in long-time service or keeping
Highly stable phase, it is thus possible to which the benefit in process is provided.
The anode active material slurry of one embodiment of the invention can further include conductive material.Above-mentioned conductive material tool
Body is carbon system substance, embodies the surface roughness of positive electrode active material layer, provides electric conductivity, as long as not making the battery inductionization
Learn variation and it is conductive, then be not particularly limited.As an example, it can be the stones such as natural graphite, artificial graphite
Ink；The carbon blacks such as carbon black, acetylene black, Ketjen black, channel black, furnace black, lampblack, thermal crack black；And carbon fibre etc..
In addition, above-mentioned conductive material can also include additional conductive material in above-mentioned carbon system substance.As one
Example can enumerate the metal systems substance such as copper, nickel, aluminium, silver, zinc, titanium；The fiber system substance of above-mentioned metal；Polyaniline
(polyaniline), polyacetylene (poly acetylene), polypyrrole (polypyrrole), polythiophene ketone
(polythiophenone) etc. electric conductive polymers etc., but not limited thereto.
At this point, the usage amount of above-mentioned conductive material is although unlimited, but contained with the total solid content of anode active material slurry
Can include 0.01~10 weight % on the basis of amount.At this point, in terms of being intended to embody the capacity characteristic that is improved, it is specific and
Speech can include 0.1~8 weight %, can include 0.5~5 weight %, but not limited thereto more specifically.
Present invention offer includes the anode of the positive electrode active material layer formed by above-mentioned anode active material slurry.
The anode of one embodiment of the invention may include being shaped as with uniform group by above-mentioned anode active material slurry
Positive electrode active material layer.In addition, above-mentioned positive electrode active material layer can be formed with high density.That is, it includes the present invention just to use
Positive electrode active material layer anode secondary cell for, due to the ionic conductivity being improved, electricity can be significantly improved
Solve the mobility of lithium ion in liquid.Therefore, even if reducing the amount of additional conductive material, the electricity being improved can also be embodied
Pond characteristic.
The anode of one embodiment of the invention can be manufactured with following methods.
Specifically, may comprise steps of：Put into adhesive and positive active material in N- ethyl-formamides and
The step of manufacturing anode active material slurry；And above-mentioned anode active material slurry is coated on positive electrode collector and drying
The step of.
For above-mentioned positive electrode collector, as long as the chemical change for neither inducing the secondary cell has high conductivity again,
It is just not particularly limited, as an example, copper, stainless steel, aluminium, nickel, titanium, calcining carbon can be used, or in aluminium or stainless steel
Positive electrode collector obtained from surface is surface-treated with carbon, nickel, titanium or silver etc..At this point, above-mentioned positive electrode collector can make
With the positive electrode collector of 3~500 μ m thicks.
Above-mentioned coating is not particularly limited, and can be carried out according to method generally known in the art.
As an example, above-mentioned coating can be above-mentioned anode active material slurry is sprayed or is allocated in it is above-mentioned just
After in electrode current collector at least one side, using scraper (doctor blade) etc. be allowed to it is evenly dispersed and carry out.
As an example, above-mentioned coating can coat (comma by die casting (die casting), comma
Coating), the methods of silk-screen printing (screen printing) carries out.
Above-mentioned drying can be the process of remaining moisture in removing step after forming positive electrode active material layer.On at this point,
Stating drying can execute in the temperature range of the degree of removal residual moisture, specifically, can be carried out at 50~200 DEG C, more
Specifically, can be carried out at 80~200 DEG C.
At this point, above-mentioned drying time is differently applied according to temperature, thus while can not uniformly determine, but can be with
Execute 1 hour or more, it is preferable that can be 5~24 hours, it is highly preferred that can be 5~12 hours.
According to the positive electrode active material layer of above method manufacture can above-mentioned positive electrode collector at least one side with 10~
100 μ m thicks are formed.Specifically, can be formed with 10~80 μm, more specifically, can be formed with 10~50 μ m thicks.
According to one embodiment of present invention, it can not only be provided notable including load deviation with very simple process
Reduce and ensure the anode of the positive electrode active material layer of uniformity, and highdensity positive electrode active material layer is provided.Therefore,
The secondary cell of anode using the present invention significantly improves the lithium ion in electrolyte due to the ionic conductivity being improved
Mobility can show excellent charge-discharge characteristic and life characteristic.
In addition, present invention offer includes the secondary cell of above-mentioned anode.
Specifically, above-mentioned lithium secondary battery may include the anode, cathode and above-mentioned anode of one embodiment of the invention
With the seperation film between above-mentioned cathode, and above-mentioned anode is formed with anode in the one side of positive electrode collector with 10~100 μ m thicks
Active material layer.
Above-mentioned lithium secondary battery anode using the present invention, thus assign the lithium ion movement being improved in electrolyte
Property, show excellent charge-discharge characteristic and life characteristic.
The initial discharge capacity of the secondary cell of one embodiment of the invention can be 200mAh/g or more.Specifically,
Initial discharge capacity can be more specifically 200~300mAh/g can be 200~250mAh/g.
Even if especially the secondary cell of one embodiment of the invention is using 50 cycles (50thCycle after), electric discharge
The variation of capacity still minimizes.Specifically, the capacity maintenance rate during above-mentioned secondary cell is recycled at 50 times can be 90%
More than.
As an example, the initial discharge capacity of above-mentioned secondary cell can be 200mAh/g or more, during 50 times recycle
Capacity maintenance rate can be 90~99%.
As an example, the initial discharge capacity of above-mentioned secondary cell can be 200mAh/g or more, and secondary cell exists
Capacity maintenance rate in 50 cycles can be 95~99%.
In addition, the C-rate efficiency that the secondary cell of one embodiment of the invention is indicated with following formula 1 can be 90% with
On.
[formula 1]
C-rate (%)=[(2C discharge capacities)/(0.1C discharge capacities)] × 100
As an example, the initial discharge capacity of above-mentioned secondary cell can be 200mAh/g or more, during 50 times recycle
Capacity maintenance rate can be 90~99%, C-rate efficiency can be 90%~99%.
As an example, the initial discharge capacity of above-mentioned secondary cell can be 200mAh/g or more, and secondary cell exists
It can be 90%~95% that capacity maintenance rate in 50 cycles, which can be 95~99%, C-rate efficiency,.
Illustrate the lithium secondary battery of one embodiment of the invention below.
The lithium secondary battery of the present invention may include anode, cathode and seperation film.
Above-mentioned anode may include the anode formed by above-mentioned anode active material slurry in positive electrode collector at least one side
Active material layer.At this point, the lithium secondary battery of the present invention can be shown as above due to including above-mentioned positive electrode active material layer
The excellent charge-discharge characteristic and life characteristic.
Above-mentioned cathode can coat the negative electrode active material pulp solution for including negative electrode active material on negative electrode collector
It dries and manufactures afterwards.At this point, above-mentioned negative electrode active material pulp solution can include following component as needed.Above-mentioned cathode
As long as the usually used substance of active material, does not just limit, as an example, difficult graphitized carbon, graphite system carbon can be enumerated
Equal carbon；LixFe2O3(0≤x≤1)、 LixWO2(0≤x≤1)、SnxMe1-xMe'yOz(Me：Mn、Fe、Pb、Ge；Me'：Al、B、
P, Si, 1 race of the periodic table of elements, 2 races, 3 race's elements, halogen；0<x≤1；1≤y≤3；1≤z≤8) etc. metal composites oxidation
Object；Lithium metal；Lithium alloy；Si system alloy；Tin system alloy；SnO、 SnO2、PbO、PbO2、Pb2O3、Pb3O4、Sb2O3、Sb2O4、
Sb2O5、GeO、GeO2、 Bi2O3、Bi2O4And Bi2O5Equal metal oxides；The electroconductive polymers such as polyacetylene；Li-Co-Ni systems
Metal composite etc..In addition, as long as above-mentioned negative electrode collector neither induces the chemical change of the secondary cell again with highly conductive
Property, then it is not particularly limited, as an example, copper, stainless steel, aluminium, nickel, titanium, calcining carbon can be enumerated, or in copper or stainless
The negative electrode collector that steel surface is surface-treated with carbon, nickel, titanium, silver etc. can be aluminium-cadmium alloy etc..Above-mentioned cathode current collection
Body is identical as positive electrode collector, both can form subtle convex-concave on surface, and strengthen the binding force of negative electrode active material, certainly
It can be formed with variforms such as film, piece, foil, net, porous body, foaming body, non-woven bodies.At this point, above-mentioned negative electrode collector can
To use the negative electrode collector of 3~500 μ m thicks.
Above-mentioned seperation film uses the insulating properties with macroion permeability and mechanical strength between positive electrode and negative electrode
Film.As an example, above-mentioned seperation film can be 5~300 μm of 0.01~10 μm of hole diameter, the thickness of seperation film
Seperation film.As long as the usually used substance of this seperation film, then do not limit, as an example, can enumerate chemical resistance and
The olefin polymers such as hydrophobic polypropylene；By the piece of the making such as coloured glaze fiber or polyethylene or non-woven fabrics etc..In addition, making
For above-mentioned electrolyte, using solid electrolytes such as polymer, solid electrolyte can also double as seperation film.
In addition, above-mentioned lithium secondary battery can further include electrolyte.
Above-mentioned electrolyte can be non-aqueous electrolyte containing lithium salt.As an example, above-mentioned non-water system containing lithium salt
Electrolyte can include non-water system organic solvent and lithium salts.One example of above-mentioned non-water system organic solvent can for example enumerate N-
N-methyl-2-2-pyrrolidone N, propylene carbonate, ethylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, γ-fourth
Lactone, 1,2- dimethoxy-ethanes, tetrahydrofuran2- methyl tetrahydrochysenes
Furans, dimethyl sulfoxide (DMSO), 1,3- dioxolanes, formamide, dimethylformamide, dioxolane, acetonitrile, nitro first
Alkane, methyl formate, methyl acetate, phosphotriester, trimethoxy-methane, dioxolane derivatives, sulfolane, methyl ring fourth
Sulfone, 1,3- dimethyl-2-imidazolinones, polypropylene carbonate ester derivant, tetrahydrofuran derivatives, ether, methyl propionateThe non-proton organic solvents such as ethyl propionate.At this point, above-mentioned non-water system organic solvent can
To be the mixed solvent selected from one or more of above-mentioned non-proton organic solvent.
As long as above-mentioned lithium salts is soluble in the substance of above-mentioned non-water system organic solvent, then do not limit.As an example,
Can be LiCl, LiBr, LiI, LiClO4、LiBF4、LiB10Cl10、LiPF6、 LiCF3SO3、LiCF3CO2、LiAsF6、
LiSbF6、LiAlCl4、CH3SO3Li、CF3SO3Li、 (CF3SO2)2NLi, chloroborane lithium, lower alphatic carboxylic acid lithium, 4- phenyl boron
Sour lithium etc., most preferably LiPF6。
In addition, above-mentioned electrolyte can be organic solid electrolyte.As an example, can be comprising selected from poly- second
Ene derivative, polyethylene oxide derivant, poly propylene oxide derivative, phosphate ester polymer, polyalginic acid salt-lysine
One or more of (agitation lysine), polyester sulfide, polyvinyl alcohol, Kynoar etc. it is ionic from
Solve the polymer of group.
In addition, above-mentioned electrolyte can be inorganic solid electrolyte.As an example, Li can be enumerated3N、LiI、
Li5NI2、Li3N-LiI-LiOH、LiSiO4、LiSiO4-LiI-LiOH、Li2SiS3、 Li4SiO4、Li4SiO4-LiI-LiOH、
Li3PO4-Li2S-SiS2Nitride, halide, the sulfate etc. of equal Li.
In addition, above-mentioned lithium secondary battery can further include additional additive.
As an example, can further include selected from pyridine, Asia for the purpose of improving charge-discharge characteristic, anti-flammability etc.
Triethyl phosphate, triethanolamine, cyclic ethers, ethylenediamine, glycol dimethyl ether (glyme), hexaphosphoric acid triamide, nitro benzenesulfonamide derivative
Object, sulphur, quinoneimine dye, N- substitutionsOxazolidone, N, N- substituted imidazoles alkane, glycol dialkyl ether, ammonium salt, pyrroles, 2-
One or more of methyl cellosolve, alchlor etc..
As an example, can also include selected from carbon tetrachloride, trifluoro-ethylene etc. for the purpose for assigning anti-flammability
Containing one or more of halogen solvent.
As an example, can also include carbon dioxide gas etc. for the purpose for assigning High temperature storage characteristic.
The lithium secondary battery of the present invention can be not only used for the battery used as the power supply of mini-plantIt can also be preferably including multiple batteriesMedium-and-large-sized battery module in be used as unit electricity
Pond.
In addition, the above-mentioned battery module of the present invention provides the battery pack for including as the power supply of medium-and-large-sized equipment, among the above
Large scale equipment can be provided including electric vehicle (Electric Vehicle, EV), mixed power electric car (Hybrid
Electric Vehicle, HEV), plug-in hybrid electric automobile (Plug-in Hybrid Electric
Vehicle, PHEV) etc. electric vehicle and electric power storing device etc., but be not limited to this.
Below by embodiment, the present invention is described in more detail.But following embodiments are for further illustrating this
Invention, not the scope of the present invention is limited by following embodiments.Following embodiments by those skilled in the art it is of course possible to being existed
It suitably revises, change in the scope of the present invention.
In addition, in the present invention without other explanation in the case of, temperature by DEG C as unit of, if without other lists
The usage amount unit of the definition of position, each ingredient is g.
(evaluation method)
1. charge/discharge capacity is evaluated
Using the secondary cell monocell (battery capacity 4.3mAh) manufactured in following embodiments and comparative example, at 25 DEG C,
In the voltage range of 3~4.5V, charge and discharge (charging by 0.5C, discharge by 1C) are carried out.
2.C-rate efficiency ratings
Using the secondary cell monocell (battery capacity 4.3mAh) manufactured in following embodiments and comparative example, in high temperature
Under environment (45 DEG C), C-rate efficiency is measured.At this point, C-rate efficiency as shown in following formula 1, is defined as to charge with 0.5C
Capacity of secondary cell when being discharged with 0.1C and capacity when being discharged with 2C ratio.
[formula 1]
C-rate (%)=[(2C discharge capacities)/(0.1C discharge capacities)] × 100
3. life characteristic is evaluated
It is defined as 50 cycles (50 of the charge and discharge measured in above-mentioned charge/discharge capacity is evaluatedthDischarge capacity) after
Discharge capacity and initial discharge capacity (1stDischarge capacity) ratio (with reference to following formula 2).
[formula 2]
Capacity maintenance rate (%)=[(discharge capacity after 50 cycles)/(initial discharge capacity)] × 100
(embodiment 1)
The LiCoO that surface is coated2Positive active material, conductive material (carbon black) and adhesive (Kynoar,
PVdF 95) are pressed:3:2 weight ratios mix and manufacture 20g, devote in N- ethyl-formamides 20g, have manufactured positive active material
Slurry (viscosity：20000g/cms, rate of change in viscosity：1%).Above-mentioned anode active material slurry is coated on 20 μm of thickness
Aluminium (Al) film as positive electrode collector of left and right after 2 hours dry at 130 DEG C, implements roll-in (roll press), system
Anode is made.Using lithium metal foil (foil) as cathode.As electrolyte, by ethylene carbonate (EC) and methyl ethyl carbonate
Ester (EMC) presses 1:2 volume ratios mix and in the non-water system organic solvents of manufacture, add LiPF6, and the LiPF6 for having manufactured 1M is non-aqueous
It is electrolyte.So that including polyethylene seperation film (Tonen companies, F2OBHE, the μ of thickness=20 between above-mentioned positive electrode and negative electrode
M), above-mentioned non-aqueous electrolyte is injected, polymer battery type experiment secondary cell monocell has been made.
Evaluate initial charge/discharge capacity, C-rate efficiency and the longevity of the secondary cell monocell of method described above manufacture
Characteristic (capacity maintenance rate) is ordered, is shown in the following table 1.
(comparative example 1)
In anode active material slurry manufacture view, N- methyl -2- pyrrolidones is used instead of N- ethyl-formamides
(NMP) it is used as solvent, has manufactured anode active material slurry (viscosity：50000g/cms, rate of change in viscosity：15%).So
Afterwards, in method identical with the method for embodiment 1, polymer battery type experiment secondary cell monocell has been made.
Evaluate initial charge/discharge capacity, C-rate efficiency and the longevity of the secondary cell monocell of method described above manufacture
Characteristic (capacity maintenance rate) is ordered, is shown in following table 1.
(table 1)
The secondary cell of the present invention not only shows significant charging capacity, but also initial discharge capacity is also in 200mAh/
G or more, capacity maintenance rate are remarkable.
Specifically, the present invention secondary cell while showing high initial discharge capacity (203.9mAh/g), really
C-rate efficiency of accepting is 91%.Especially secondary cell of the invention, it is thus identified that capacity maintenance rate 97%.This hair
The high power capacity sustainment rate of bright secondary cell compared with comparative example, be equivalent to reach 114% or more remarkable result.
The preferred embodiment of the present invention is illustrated above, but present invention is not limited to this, in claims and
In the range of specification, various deformation can be carried out and implemented, this also belongs to the scope of the present invention certainly.
Claims (12)
1. a kind of secondary battery anode active compound coating solvent is comprising N- ethyl-formamides.
2. a kind of anode active material slurry is comprising positive active material, adhesive and N- ethyl-formamides.
3. anode active material slurry according to claim 2, wherein the positive active material is with following chemical formula 1
It indicates：
Chemical formula 1
Li1+x[NiaCobMnc]O2
In the chemical formula 1, -0.5≤x≤0.6,0≤a, b, c≤1, x+a+b+c=1.
4. anode active material slurry according to claim 2, wherein described adhesive is selected from fluorine system adhesive and rubber
It is adhesive.
5. anode active material slurry according to claim 2, wherein using anode active material slurry total weight as base
The solid component content of standard, the anode active material slurry is 30~80 weight %.
6. anode active material slurry according to claim 5, wherein with the total solid content of anode active material slurry
On the basis of content, the positive active material is 55~99 weight %.
7. anode active material slurry according to claim 2, wherein also include conductive material.
8. anode active material slurry according to claim 7, wherein the conductive material is carbon system substance.
9. a kind of anode, wherein include being formed just by the anode active material slurry described in any one of claim 2~8
Pole active material layer.
10. a kind of secondary cell, wherein including between anode, cathode and the positive and described cathode described in claim 9
Seperation film,
And the anode forms positive electrode active material layer in the one side of positive electrode collector with 10~100 μm of thickness.
11. secondary cell according to claim 10, wherein initial discharge capacity is 200mAh/g or more, 50 cycles
In capacity maintenance rate be 90% or more.
12. secondary cell according to claim 10, wherein the C-rate efficiency indicated with following formula 1 is 90% or more,
Formula 1
C-rate (%)=[(2C discharge capacities)/(0.1C discharge capacities)] × 100.
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| KR20170027406 | 2017-03-03 | ||
| KR10-2017-0027406 | 2017-03-03 | ||
| KR1020180021771A KR102548586B1 (en) | 2017-03-03 | 2018-02-23 | Solvent for coating positive electrode material of secondary battery, positive electrode material slurry comprising the same and secondary battery prepared therewith |
| KR10-2018-0021771 | 2018-02-23 |
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Also Published As
| Publication number | Publication date |
|---|---|
| JP2018147882A (en) | 2018-09-20 |
| CN108539198B (en) | 2023-02-28 |
| JP7138455B2 (en) | 2022-09-16 |
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