CN106063013A - Battery anode with preloaded metals - Google Patents
Battery anode with preloaded metals Download PDFInfo
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- CN106063013A CN106063013A CN201580011664.0A CN201580011664A CN106063013A CN 106063013 A CN106063013 A CN 106063013A CN 201580011664 A CN201580011664 A CN 201580011664A CN 106063013 A CN106063013 A CN 106063013A
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- 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
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
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- 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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- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
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- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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- H01M4/02—Electrodes composed of, or comprising, active material
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- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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Abstract
A method is presented for fabricating an anode preloaded with consumable metals. The method provides a material (X), which may be one of the following materials: carbon, metals able to be electrochemically alloyed with a metal (Me), intercalation oxides, electrochemically active organic compounds, and combinations of the above-listed materials. The method loads the metal (Me) into the material (X). Typically, Me is an alkali metal, alkaline earth metal, or a combination of the two. As a result, the method forms a preloaded anode comprising Me/X for use in a battery comprising a M1yM2z(CN)n .mH2O cathode, where M1 and M2 are transition metals. The method loads the metal (Me) into the material (X) using physical (mechanical) mixing, a chemical reaction, or an electrochemical reaction. Also provided is preloaded anode, preloaded with consumable metals.
Description
Technical field
Present invention relates generally to electrochemical cell, and relate more specifically to preload and have anode and the phase of consumption type metal
The manufacturing process closed.
Background technology
Rechargeable lithium ion batteries (LIB) has caused just because of its high power density, long circulation life and Environmental compatibility
Portable electronic apparatus revolution.Chargeable LIB is by by Li+Negative electrode (positive pole) and anode (negative pole) that ion permeable membrane separates form.
The solution containing lithium ion or polymer is the most also used to make Li+Ion can freely come between positive pole and negative pole
Return " rocking ".Positive electrode is usually transition metal oxide such as cobalt acid lithium (LiCoO2), LiMn2O4 (LiMn2O4), LiFePO4
(LiFePO4) and their derivant.Lithium ion freely and reversibly can move in their gap.Negative material is permissible
Use lithium metal, alloy and carbonaceous material.During discharging, Li+Ion is extracted from negative pole and is inserted in positive pole.With
Time, electronics and produces electric power by external circuit from negative pole to positive pole.During charging, ion and electronics are in the opposite direction
Move and return the position of its original.
Though the use that LIB has succeeded, lithium demand rare with lithium between conflict and make LIB cost rise violently, this
Hinder the further large-scale application of lithium ion battery.Therefore, the low cost needing the succedaneum as expensive LIB badly can be filled
Electricity battery.In this case, sodium-ion battery is the most more paid close attention to, because sodium has the character closely similar with lithium,
But cost is lower.As lithium ion battery, sodium-ion battery needs Na+Material of main part is as their electrode.Spend
A lot of effort are to use the Na for sodium-ion battery+Main-body electrode material directly replicates Li+Agent structure.Such as,
Develop for sodium-ion battery and be respectively provided with and LiCoO2The NaCoO of similar layer structure2、NaMnO2、NaCrO2With
Na0.85Li0.17Ni0.21Mn0.64O2.Similarly, have employed in sode cell there is the Co of spinel structure3O4, have
The Na of NASICON structure3V2(PO4)3, and there is the NaFePO of olivine structural4.It addition, sodium fluorophosphate such as Na2PO4F、
NaVPO4F and Na1.5VOPO4F0.5Also the positive pole in sode cell it is utilized as.
But, for Na+Or K+For host compound, replicate Li+The structure of host compound is unpractical.Sodium
Ion and potassium ion are more much bigger than lithium ion, and serious distortion Li+The structure of host compound.Therefore, for sodium ions to potassium ions
Improving it is very important that exploitation has the new of the wide arc gap that wherein sodium ions to potassium ions can easily and reversibly move of battery
Na+/K+Material of main part.Have been observed that Na+/K+Ion is embedded in metal cyanide compound.
Fig. 1 is for describing the figure (prior art) of the crystal structure of six cyano metal acid metal salt (MHCM).MHCM can be with table
It is shown as AxM1yM2z(CN)n.mH2O, wherein A can be selected from, but not limited to, alkali and alkaline earth metal ions, and M1 and M2 is transition gold
Belong to such as titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), ferrum (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), calcium (Ca), magnesium
(Mg) etc..M1 and M2 can be same or different metal.According to material therefor, the ratio (x:n) of M1 with M2 is variable.Have
The transition metal hexacyanoferrate (TMHCF) of wide arc gap is the most carried out as the cathode material for rechargeable battery
Research.TMHCM can be expressed as M1yM2z(CN)n·mH2O。
For cathode material, for both LIB and MeIB, various materials are all available, and wherein Me is metal such as sodium
(Na), potassium (K), magnesium (Mg), calcium (Ca), caesium (Cs) or aluminum (Al), different from cathode material, the selection of anode material is to have very much
Limit, for MeIB.At present, graphite is the anode material being most widely used for LIB.Its layer structure permits
Permitted the lithium between carbon-coating to embed, and this reaction be can be written as follows:
Li++C6+e→LiC6
This insertion reaction is to Li+/ Li is that 0.2V occurs below, and has good reversibility, follows for the first time
Ring causes the initial irreversible capacity of about 12%.It is to be noted, however, that true as follows: non-lithium Mea+Graphite can not be inserted
In Ceng, because it has more than Li+Size.As a result, the anode material substituted it is highly desirable to when developing chargeable MeIB.With
As a example by the anode material of SIB, hard carbon or so-called " difficult graphitization " carbonaceous material are candidate item.Poor big with having
The graphite of Me (such as sodium) ion storage performance is different, gives the credit to the fake capacitance (pseudocapacitive) on hard carbon surface
Me ionic adsorption, hard carbon can last up to the capacity of 300 MAH every gram (mAh/g).The group of Dahn is prepared for being derived from not
With the various hard carbon anodes of low cost organic precursor and in both LIB and SIB, have rated their anode performance [non-specially
Profit document 1,2].They further disclose the sodium in hard carbon anode and insert mechanism [non-patent literature 3,4].Except occurring at high electricity
Beyond telescopiny under the scope of position, insert in graphene layer corresponding with sodium, issue in the electronegative potential scope close to sodium metal
Show the filling in the micropore on hard carbon surface.In circulation for the first time, these reaction only parts are reversible, therefore cause big
In the big irreversible capacity of 30%.Sodium oxide the most embedding to other anode material, alloy and organic compound are at SIB
In potential application studied.Find the zero strain anode material Li for LIB4Ti5O12Three are experienced during sodium embeds
Phase reaction [non-patent literature 5].After activation process in 20 times initial circulations, the reversible appearance of its display 150mAh/g
Amount.But, its Initial Coulombic Efficiencies is only 81%.The group of Tarascon reports the Na as low-voltage anode2Ti3O7, its
There is in the embedding sodium compound of non-carbon minimum removing sodium (desodiation) current potential.But, its reversible capacity is more than 40%
[non-patent literature 6].High reversible capacity (> 500mAh/g can be had with metal such as stannum, antimony and the lead of sodium formation alloy), but,
They display that initial capacity loss [non-patent literature 7,8] of about 20% in circulation for the first time.Recently, Hong etc. and Hu etc.
Confirm at organic anode Na2C8H4O4In reversible Na+Insertion behavior, this organic anode shows in low voltage range
The reversible capacity [non-patent literature 9,10] of 300mAh/g.As other anode material, this organic anode is in circulation for the first time
The reversibility of middle display difference.In addition to the use in SIB of these anode materials, it is believed that due to similar electrochemical reaction,
They may display that big irreversible capacity in the case of other metal battery during circulation for the first time.
Prior art literature
Non-patent literature
Non-patent literature 1:D.A.Stevens, J.R.Dahn, for the high power capacity anode material of chargeable sodium-ion battery
(High Capacity Anode Materials for Rechargeable Sodium-ion Batteries), electrochemistry
Association's magazine (J.Electrochem.Soc.) 147 (2000) 1271.
Non-patent literature 2:Edward Buiel, J.R.Dahn, for the hard carbon sun prepared from sucrose of Li ion battery
Reduction (the Reduction of The Irreversible Capacity in Hard-of the irreversible capacity of pole material
Carbon Anode Materials Prepared from Sucrose for Li-ion Batteries), ECS
Magazine 145 (1998) 1977.
Non-patent literature 3:D.A.Stevens, J.R.Dahn, lithium and sodium insert the mechanism (The in material with carbon element
Mechanism of Lithium and Sodium Insertion in Carbon Materials), ECS's magazine
148(2001)A803。
Non-patent literature 4:D.A.Stevens, J.R.Dahn, in the electrochemical cell of work, sodium inserts nanoporous carbon
Original position small angle X ray scattering research (the An in-situ Small-Angle X-ray Scattering Study of anode material
of Sodium Insertion into A Nanoporous Carbon Anode Material within An
Operating Electrochemical Cell), ECS's magazine 147 (2000) 4428.
Non-patent literature 5:Yang Sun, Liang Zhao, Huilin Pan, Xia Lu, Lin Gu, Yong-Sheng
Hu, Hong Li, Michel Armand, Yuichi Ikuhara, Liquan Chen, Xuejie Huang, for room temperature sodium
The direct atom level of the three-phase Ultrahigh in the Li4Ti5O12 anode of ion battery confirms (Direct Atomic-scale
Confirmation of Three-phase Storage Mechanism in Li4Ti5O12 Anodes for Room-
Temperature Sodium-ion Batteries), natural communication (Nat.Comm.) 4 (2013) 1870.
Non-patent literature 6:P.Senguttuvan, G.Rousse, V.Seznec, J.M.Tarascon, M.R.Palacin,
The oxide for sodium-ion battery of Na2Ti3O7: the minimum voltage once reported inserts electrode (Na2Ti3O7:Lowest
Voltage Ever Reported Oxide Insertion Electrode for Sodium Ion Batteries), material
Material chemistry (Chem.Mater.) 23 (2011) 4109.
Non-patent literature 7:M.K.Datta, R.Epur, P.Saha, K.Kadakia, S.K.Park, P.N.Kumta, stannum and
Graphite based nanometer complex: for potential anode (the Tin and graphite based of sodium-ion battery
Nanocomposites:Potential Anode for sodium ion batteries), power supply magazine (J.Power
Sources),225(2013)316。
Non-patent literature 8:Y.Zhu, X.Han, Y.Xu, Y.Liu, S.Zheng, K.Xu, L.Hu, C.Wang, for stable
And electrostatic spinning Sb/C fiber (the Electrospun Sb/C Fibers for a Stable of quick sodium-ion battery anode
And Fast Sodium-Ion Battery Anode), ACS nanometer (ACS Nano), 7 (2013) 6378.
Non-patent literature 9:Y.Park, D.S.Shin, S.H.Woo, N.S.Choi, K.H.Shin, S.M.Oh, K.T.Lee,
S.Y.Hong, as terephthalic acids sodium (the Sodium terephthalate as of the organic anode material for sodium-ion battery
An organic Anode material for sodium ion batteries), advanced material (Adv.Mater.), 24
(2012)3562。
Non-patent literature 10:A.Abouimrane, W.Weng, H.Eltayeb, Y.Cui, J.Niklas,
O.Poluektov, K.Amine, the sodium in carboxylation composition material inserts and carboxylation composition material answering in the full sode cell of 3.6V
With (Sodium insertion in carboxylate based materials and their application in
3.6 V full sodium cells), energy environment science (Energy Environ.Sci.), 5 (2012) 9632.
Non-patent literature 11:M.E.Leonova, I.K.Bdikin, S.A.Kulinich, O.K.Gulish,
Phase transition under high pressure (the High-Pressure of L.G.Sevast`yanova, K.P.Burdina, six side's alkali metal pnictide
Phase Transition of Hexagonal Alkali Pnictides), inorganic material (Inorg.Mater), 39
(2003)266。
Summary of the invention
Technical problem
Due to the irreversible reaction in anode-side i.e. solid electrolyte interface (SEI) formed consume from negative electrode metal from
Son, result causes the energy of full battery to be remarkably decreased.Therefore, the target of the irreversible capacity reducing these anodes becomes MeIB and opens
Significant challenge in Faing.
Technical scheme
According to an aspect of the present invention, it is provided that a kind of for manufacturing the method that preload has the anode of consumption type metal,
Described method includes: provide select free carbon, can with the metal of metal (Me) electrochemically alloying, embed oxide
In the group of the combination composition of (intercalation oxide), electro-chemical activity organic compound and material listed above
Material (X)；Described metal (Me) is loaded to described material (X), wherein Me select free alkali metal, alkaline-earth metal and alkali metal and
The group of the combination composition of alkaline-earth metal；Formation is used for comprising M1yM2z(CN)n·mH2The pre-of Me/X that comprise of the battery of O negative electrode is born
The anode carried；Wherein M1 and M2 is transition metal；Wherein y is less than or equal to 1；Wherein z is less than or equal to 1；Wherein n less than or etc.
In 6；And wherein m is less than or equal to 20.
According to an aspect of the present invention, it is provided that a kind of preload has the anode of the preload of consumption type metal, described pre-
The anode of load comprises: conductive current collector；With cover described current collector Me/X, wherein X for select free carbon, can be with metal (Me)
The combination composition of the metal of electrochemically alloying, embedding oxide, electro-chemical activity organic compound and material listed above
Group in material, and Me be select free alkali metal, alkaline-earth metal and alkali and alkaline earth metal ions combination composition group in
Metal.
According to an aspect of the present invention, it is provided that a kind of have the electricity of preload that preload has the anode of consumption type metal
Pond, the battery of described preload comprises: electrolyte；The anode of preload, it comprises: conductive current collector；Cover described current collector
Me/X, wherein X be select free carbon, can with the metal of metal (Me) electrochemically alloying, embed oxide, electro-chemical activity and have
Material in the group of the combination composition of machine compound and material listed above, and Me is for selecting free alkali metal, alkaline-earth metal
And the metal in the group of the combination composition of alkali and alkaline earth metal ions；Negative electrode, it comprises: conductive current collector；Cover described current collection
The M1 of deviceyM2z(CN)n·mH2O；Wherein M1 and M2 is transition metal；Wherein y is less than or equal to 1；Wherein z is less than or equal to 1；
Wherein n is less than or equal to 6；Wherein m is less than or equal to 20；And the described electrolysis of immersion being placed between described anode and described negative electrode
Ion permeable membrane in matter.
Beneficial effect
If anode can be manufactured with the state of preload to keep big reversible appearance when this anode is used in the battery
Amount, will be favourable.
Accompanying drawing explanation
[Fig. 1] Fig. 1 is the figure (prior art) of the crystal structure describing six cyano metal acid metal salt (MHCM).
[Fig. 2] Fig. 2 is the partial cross section view that preload has the anode of the preload of consumption type metal.
[Fig. 3] Fig. 3 is the partial cross section view of the battery of the preload with the anode that preload has consumption type metal.
[Fig. 4] Fig. 4 is the partial cross section view describing the form preload Me metal with integrated particle.
[Fig. 5] Fig. 5 is the partial cross section view describing the form preload Me metal with metallic diaphragm.
[Fig. 6] Fig. 6 is to describe about comprising the hard carbon anode being mixed with sodium metal and Berlin green negative electrode (FeFe (CN)6)
The voltage of sodium-ion battery is relative to the figure of capacity.
[Fig. 7] Fig. 7 is the figure describing the voltage about the half-cell using sodium anode and antimony negative electrode relative to capacity.
[Fig. 8] Fig. 8 is to show for manufacturing the flow chart of method that preload has the anode of consumption type metal.
Detailed description of the invention
Disclosed herein for the anode material made with the metal of preload for high-performance metal ion battery (MeIB)
Material, the most such as Me can be such as sodium (Na), potassium (K), calcium (Ca), magnesium (Mg), caesium (Cs) or the metal of aluminum (Al).Described metal
Can physically, chemically or electrochemically load to another kind of active material of positive electrode such as carbon, can with Me alloyed metal (AM),
Embed oxide, electro-chemical activity organic compound or containing at least one complex (composite) of the above.Example
As, make it possible for the negative electrode without sodium at anode-side preload sodium, and the more important thing is, eliminate by the earlier cycles stage
The irreversible capacity that the irreversible reaction of middle generation causes.Drawing analogous conclusions, the advantage of preload sodium-ion battery (SIB) can expand
Open up to other MeIB.
Anode material comprises Me, and it promotes and the electrochemical reaction of at least one in following non-Me metal material: hard carbon
(or so-called " difficult graphitized carbon ")；Comprise in antimony (Sb), stannum (Sn), lead (Pb), phosphorus (P), sulfur (S), silicon (Si) or selenium (Se)
The metal or alloy of at least one；The intercalation compound such as (but not limited to) Li of Me ion4Ti5O12、Na4Ti5O12、Na3Ti2O7、
NaX[Li1-YTiY]O2；With organic carboxylation composition material such as (C8H4Na2O4)、(C8H6O4)、(C8H5NaO4)、(C8Na2F4O4)、
(C10H2Na4O8)、(C14H4O6) and (C14H4Na4O8).Other electro-chemical activity non-Me metal ingredient as main body can be passed through
The carbon of the most pre-sodium (presodiated) or alloy accommodate the Me of preload.Can be by Me particle be mechanically embedded in it
Its anode components realizes the preload of Me.This process can relate to dry type and the auxiliary spray of wet processed both techniques such as electrostatic
Painting, thermal spraying, mechanical mixture and various printing process.Additionally, by making metal Me react with the reducing agent containing Me or pass through
Electrochemical reaction can chemically preload metal Me.
Therefore it provides it is a kind of for manufacturing the method that preload has the anode of consumption type metal.Described method provides material
(X), material (X) can be the one in following material: carbon, can with the metal of metal (Me) electrochemically alloying, embed oxidation
Thing, electro-chemical activity organic compound and the combination of material listed above.Metal (Me) is loaded to material by described method
(X).Typically, Me is typically alkali metal, alkaline-earth metal or combination.More clearly, Me can be lithium (Li), sodium
(Na), potassium (K), rubidium (Rb), caesium (Cs), calcium (Ca), terbium (Tb), strontium (Sr), barium (Ba), silver (Ag), aluminum (Al) or magnesium (Mg).Knot
Really, described method is formed and is used for comprising M1yM2z(CN)n·mH2The anode of the preload comprising Me/X of the battery of O negative electrode；Its
Middle M1 and M2 is transition metal；Wherein y is less than or equal to 1；Wherein z is less than or equal to 1；Wherein n is less than or equal to 6；And its
Middle m is less than or equal to 20.
As it has been described above, described method uses physics (mechanical) mixing, chemical reaction or electrochemical reaction to be born by metal (Me)
It is downloaded to material (X).M1 and M2 is for obtaining the transition metal such as titanium (Ti) of (need not identical), vanadium (V), chromium independently of one another
(Cr), manganese (Mn), ferrum (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), calcium (Ca) or magnesium (Mg).
Also provide for the anode that preload has the preload of consumption type metal.The anode of described preload is by having covering current collection
The conductive current collector of the Me/X of device is formed, and wherein Me and X material is described above.Additionally provide has consumption for having preload
The battery of the preload of the anode of property metal.Described battery by electrolyte, the anode of above-mentioned preload, by having covering current collector
M1yM2z(CN)n·mH2Negative electrode that the conductive current collector of O is made and immersing in electrolyte of being placed between anode and negative electrode
Ion permeable membrane is made.
The more details of the battery of following description said method, the anode of preload and preload.
Fig. 2 is the partial cross section view that preload has the anode of the preload of consumption type metal.The anode 200 of preload wraps
Containing conductive current collector 202 and the Me/X 204 of covering current collector 202.X be such as carbon, can be with metal (Me) electrochemically alloying
The material of the combination of metal, embedding oxide, electro-chemical activity organic compound and material listed above.Me is metal, allusion quotation
It is alkali metal, alkaline-earth metal or combination type.More clearly, Me can be lithium (Li), sodium (Na), potassium (K), rubidium
(Rb), caesium (Cs), calcium (Ca), terbium (Tb), strontium (Sr), barium (Ba), silver (Ag), aluminum (Al), magnesium (Mg) or the combination of these metals.
Some clear and definite examples of Me/X material include LirVO2, wherein 0 < r < 1；NasMnO2, wherein 0 < s < 1；Na-Sn closes
Gold；Lithium powder and the mixture of stannum particle；Sodium particle and the mixture of hard carbon powder；Hard carbon and the complex of lithium；Hard carbon and sodium
Complex；Li-Sn alloy；Li-Sb alloy；Na-Sb alloy；Fe3O4Complex with Li；And Fe3O4Complex with Na.
It should be understood, however, that the sub-fraction of this possible material simply listed.
Fig. 3 is the partial cross section view of the battery of the preload with the anode that preload has consumption type metal.Preload
Battery 300 comprise the anode 200 of electrolyte 302 and as above preload described in the explanation of Fig. 2.At this for brevity
Do not repeat the details of the anode of preload.The battery 300 of preload also comprises by conductive current collector 306 and covers current collector
M1yM2z(CN)n·mH2The negative electrode 304 that O 308 makes；Wherein M1 and M2 is transition metal；Wherein y is less than or equal to 1；Wherein z
Less than or equal to 1；Wherein n is less than or equal to 6；And wherein m is less than or equal to 20.
Ion permeable membrane 310 is dipped in electrolyte 302, and is placed between anode 200 and negative electrode 304.As it has been described above,
M1 and M2 obtains independently of one another, and can be Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ca or Mg.
Polymer adhesive (not shown) such as politef (PTFE) or polyvinylidene fluoride (PVDF) can be used to carry
Adhesion between power pole material and current collector, thus improve overall physical stability.
Electrolyte 302 can be non-aqueous, such as liquid organic electrolyte or gel electrolyte, polymer dielectric, solid
Body (inorganic) electrolyte etc..The Common examples of non-aqueous (liquid) electrolyte includes organic carbonate such as ethylene carbonate (EC), carbon
The sub-propyl ester (PC) of acid, diethyl carbonate (DEC) etc., but there is also other organic carbonates many and the replacement of organic carbonate
Product.Typically, gel electrolyte is made up of swelling in the presence of liquid electrolyte polymeric material.As gel electricity
The example of the polymer solving matter includes but not limited to poly(ethylene oxide) (PEO) and fluorinated polymer such as polyvinylidene fluoride (PVDF)
Base polymer and copolymer etc..By contrast, although swelling in liquid electrolyte of polymer is left out, but can make
(solid) polymer dielectric is prepared with the polymer with the polymer same type for forming gel electrolyte.Finally, may be used
To consider solid inorganic (or pottery) material as electrolyte, material can be with liquid electrolytic for described solid inorganic (or pottery)
Matter is applied in combination.Generally speaking, suitable electrolyte system can be with various structures by above type of combination of materials (mixing)
Composition.In the case of some is unshowned, as may be in the case of polymer gel, polymer and solid electrolyte, ion
Permeable membrane 310 can be identical material with electrolyte 302.
Generally, composite anode (negative pole) material comprise preload Me and for metal ion battery (MeIB) non-Me gold
Belonging to (X) anode material, wherein Me can for example, Na, K, Ca, Cs, Mg or Al.The electric discharge that complex contains in MeIB is (de-
Embedding) Me of preload that can extract from main body non-Me metal ingredient X during process, thus eliminate by conventional non-Me gold
Belong to the initial irreversible capacity of anode introducing and make it possible for the cathode material without Me.
Although compared with non-metallic anode material, Me metal anode because of its low anode potential in metal ion battery
There is the highest theoretical capacity and the highest energy density is provided, but due to such as dendritic growth during circulating and height
Chemically reactive safety problem, it is unpractical for using sodium or potassium metal in commercial battery.It is therefore contemplated that non-metallic material
Material is the optimum selection of metal ion battery Anodic.But, as in sodium-ion battery, as above in background technology portion
Mentioned by Fen, all conventional non-metallic anodes are respectively provided with big irreversible capacity because of its initial charge/discharge process.Simply
Ground is said, asks by the Me preload of electro-chemical activity is solved this to non-Me metal (X) anode material (can be write as Me/X)
Topic, the one during wherein X can be aforementioned non-Me metal anode material or combinations thereof.When preload Me metal, Me gold
Belong to the side reaction consumption formed such as solid electrolyte interface (SEI), or integrated with non-Me metal anode by embedding.Therefore,
After some initial charge cycle without Me metal for good and all remaining in the anode.
Fig. 4 is the partial cross section view describing the form preload Me metal with integrated particle.Non-Me metal anode material
400 cover current collector 402 together with the particle 404 containing Me of preload.Binding agent and conductive agent 406 can also be there is.Filling
After electricity circulation, form Me/X material 408, during wherein Me metal is integrated into non-Me metal anode equably.
Fig. 5 is the partial cross section view describing the form preload Me metal with metallic diaphragm.Non-Me metal level 500 covers
Current collector 502.The Me layer 504 of preload covers non-Me metal level 500.After charging cycle, form Me/X material 506, wherein
Me metal is integrated in non-Me metal anode equably.
Can be by mixing Me with X, by with the reducing agent reduction X containing Me or being prepared by electrochemical reaction process
Me/X.For example, it is possible to by sodium particle is integrated in hard carbon substrate or in the nonaqueous electrolyte containing sodium salt electrochemically
Sodium is inserted in hard carbon, prepare Na/ hard carbon complex.On the one hand, can be prepared by mechanically mixed sodium and Sb particle
Na/Sb complex.On the other hand, at a temperature of raising, Na is formed in an inert atmospherexSb alloy.
As the mode of the anode of explanation preload, presented below based on comprising Na/X anode and the sodium ion of different negative electrode
Two examples of the battery applications of battery.
Fig. 6 is to describe about comprising the hard carbon anode being mixed with sodium metal and Berlin green negative electrode (FeFe (CN)6) sodium from
The voltage of sub-battery is relative to the figure of capacity.During for the first time electric discharge, at the sodium metal of preload of anode-side as anode,
And embed in Berlin green negative electrode.In charging process subsequently, sodium is removed from Berlin green and is inserted in hard carbon.As
Shown in figure, after circulating at 3 times, the sodium of preload has been totally consumed and has obtained to have based on cathode quality and has been more than
The Berlin green of the capacity of 130mAh/g/hard carbon sode cell.It should be noted that the sodium carrying method using other is as electrochemically
Sodium is inserted hard carbon can realize identical battery behavior.
Fig. 7 is the figure describing the voltage about the half-cell using sodium anode and antimony negative electrode relative to capacity.At battery
For the first time in circulation, Sb experiences alloying reaction during discharging, and forms Na at the end of electric discharge3Sb.Although achieving
More than the high power capacity of 800mAh/g, but reversible capacity is only 600mAh/g, is equivalent to the initial discharge capacity of 75%.The most not
Reversible capacity is formed owing to SEI layer, it means that electrolyte is reduced electrochemically on the surface of anode.Ask to solve this
Topic, can obtain the anode Na of preload by heating sodium and antimony under 850 degrees Celsius in Ar atmosphere3Sb alloy is [non-specially
Profit document 11], and at Na3The sodium of the preload in Sb makes once electrolyte contact Na3Sb just can form SEI layer.Cause
This, can eliminate the big irreversible capacity shown in figure.
Therefore, the anode being made up with non-Me metal active material of the Me of preload eliminates relevant to conventional anode materials
Irreversible capacity and make it possible for the cathode material without Me.As a result, the chargeable Me ion battery of safety can obtain
Obtain high power capacity and long circulation life.
Fig. 8 is to show for manufacturing the flow chart of method that preload has the anode of consumption type metal.Although for understand
See that the method is depicted as a series of numbering step, but numbering is not necessarily indicative to the order of step.It should be understood that in these steps
Some can be omitted, parallel carry out or keep carrying out in the case of exact sequence not requiring.But, usual described method
Follow the numerical order of described step.Described method is from the beginning of step 800.
Step 802 provides material (X), its can be carbon, can be (the most non-with the metal of metal (Me) electrochemically alloying
Me metal), embed oxide, electro-chemical activity organic compound or the combination of material listed above.Some clear and definite examples
Including the metal or alloy containing at least one in Sb, Sn, Pb, P, S, Si or Se, Me ion is intercalation compound as (but do not limited
In) Li4Ti5O12、Na4Ti5O12、Na3Ti2O7、Nax[Li1-yTiy]O2；With organic carboxylation composition material such as (C8H4Na2O4)、
(C8H6O4)、(C8H5NaO4)、(C8Na2F4O4)、(C10H2Na4O8)、(C14H4O6) and (C14H4Na4O8).Step 804 is by metal
(Me) material (X) is loaded to.Generally, Me is alkali metal, alkaline-earth metal or combination.More clearly, Me can be lithium
(Li), sodium (Na), potassium (K), rubidium (Rb), caesium (Cs), calcium (Ca), terbium (Tb), strontium (Sr), barium (Ba), silver (Ag), aluminum (Al) or magnesium
(Mg)。
Step 806 is formed and is used for comprising M1yM2z(CN)n·mH2The sun of the preload comprising Me/X of the battery of O negative electrode
Pole；Wherein M1 and M2 is transition metal；Wherein y is less than or equal to 1；Wherein z is less than or equal to 1；Wherein n is less than or equal to 6；And
And wherein m is less than or equal to 20.
Typically, M1 and M2 obtains independently of one another, it means that they can be identical or different metal.M1 and M2
Some examples of metal include titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), ferrum (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc
(Zn), calcium (Ca) and magnesium (Mg).
In one aspect, step 808 consumes the metal (Me) in the anode of preload, and step 810 is formed and comprises material
The stable anode of material (X).In one aspect, the active material in anode is made up of X material completely.
Step 804 uses physics (mechanical) mixing, chemical reaction or electrochemical reaction process that metal (Me) is loaded to material
Material (X).Step 804 can be by using chemical reaction that metal (Me) is loaded to material with the reducing agent reduction X containing Me
(X).Then, the anode forming preload in step 806 includes forming Me/X (MeX) compound, wherein Me and Xization
Learn reaction.Reduce some examples of X with the reducing agent containing Me to include the following: and reduce VO with n-BuLi2To form LirVO2,
Wherein 0 < r < 1；With the NaH reduction MnO of tert-butyl group alkoxide activation in oxolane2Form NasMnO2, wherein 0 < s < 1；Use NaH
Reduction TiO2Form NaTiO2；With by Sn mix particles fusing Na in formed Na-Sn alloy.These examples are not reduction works
Skill and the complete list of material.
In yet another aspect, whether step 804 passed through in the case of or not causing chemical reaction between Me and X particle in inertia
Atmosphere mechanically mixes Me and X particle and uses physical mixed that metal (Me) is loaded to material (X).Mechanically mixing Me and
Some examples of X particle include: in an ar atmosphere by ball milling mixing lithium powder and stannum particle；With more than 100 degrees Celsius
At a temperature of in industrial mixer mixed sodium particle and hard carbon powder, be then cooled to room temperature.Physical mixed technique can use
The auxiliary spraying of both dry type and wet processed technology such as electrostatic, thermal spraying, mechanical mixture and various printing process.Can also use
Other NM hybrid technique and material.
In one aspect, step 804 uses following sub-step, by electrochemical reaction, metal (Me) is loaded to material
(X).Step 804a formed the electrode of X and Me to electrode, both of which is inserted in electrolyte.Such as, X can be hard carbon, stannum,
Antimony, Na2Ti3O7、Li4Ti5O12, or Fe3O4, and Me can be lithium or sodium.
Step 804b carries out repeatedly discharge and recharge operation, and wherein charging operations uses external power source to generate from described electrode to institute
State the positive voltage current potential to electrode.Discharge operation is connected external loading at described electrode between to electrode；Fill in response to described
Discharge operation, Me particle is inserted material (X) by step 804c.Then, the anode forming preload in step 806 includes being formed
Me/X (Me/X) compound, wherein Me Yu X has carried out chemical reaction.
In yet another aspect, step 804 uses electrochemistry by making Me with X directly contact in Me ionic conduction solution
Metal (Me) is loaded to material (X) by reaction.Again, the anode of the preload formed in step 806 comprises Me/X (MeX) and changes
Compound, wherein Me Yu X has carried out chemical reaction.
Have been presented for concrete material and process the example of step so that the present invention to be described.But, the present invention not only limits to
In these examples.Those skilled in the art are it is appreciated that other variant of the present invention and embodiment.
By way of reference following all applications are incorporated herein: (1) has the metal battery electrode of pyrolytic coating
(METAL BATTERY ELECTRODE WITH PYROLYZED COATING), is invented by Yuhao Lu etc., serial number 14/
On February 28th, 193,782,2014 submits to, attorney docket SLA3353；(2) there are six cyano metal acid metals of shielding construction
Salt electrode (METAL HEXACYANOMETALLATE ELECTRODE WITH SHIELD STRUCTURE), by Yuhao Lu etc.
Invention, serial number 14/193,501, submit on February 28th, 2014, attorney docket SLA3352；(3) cyano metal acid-salt negative electrode
Battery and manufacture method (Cyanometallate Cathode Battery and Method for Fabrication), by
Yuhao Lu etc. invent, serial number 14/174,171, and on February 6th, 2014 submits to, attorney docket SLA3351；(4) ferrous
(II)-six cyano ferrum (II) acid sode cell electrode and synthetic method (SODIUM IRON (II)-HEXACYANOFERRATE (II)
BATTERY ELECTRODE AND SYNTHESIS METHOD), Yuhao Lu etc. invent, serial number 14/067,038,
On October 30th, 2013, attorney docket SLA3315；(5) transition metal six cyano metal acid-salt-conductive polymer composite
(TRANSITION Metal HexacyanoMETALLATE-CONDUCTIVE POLYMER COMPOSITE), by Sean
Vail etc. invent, serial number 14/059,599, and on October 22nd, 2013 submits to, attorney docket SLA3336；(6) metal-doped
Transition metal hexacyanoferrate (TMHCF) battery electrode (Metal-Doped Transition Metal
Hexacyanoferrate (TMHCF) Battery Electrode), Yuhao Lu etc. invent, serial number 13/907,892,
On June 1st, 2013 submits to, attorney docket SLA3287；(7) with the Hexacyanoferrate that ferrocyanide or the iron cyanide are modified
Salt battery electrode (HEXACYANOFERRATE BATTERY ELECTRODE MODIFIED WITH FERROCYANIDES OR
FERRICYANIDES), inventing, serial number 13/897,492 by Yuhao Lu etc., on May 20th, 2013 submits to, attorney docket
SLA3286；(8) shielded transition metal hexacyanoferrate battery electrode (PROTECTED TRANSITION METAL
HEXACYANOFERRATE BATTERY ELECTRODE), Yuhao Lu etc. invent, serial number 13/872,673,2013 4
The moon 29 was submitted to, attorney docket SLA3285；(9) there is the transition metal hexacyanoferrate electricity of single platform charging and discharging curve
Pool cathode (TRANSITION METAL HEXACYANOFERRATE BATTERY CATHODE WITH SINGLE PLATEAU
CHARGE/DISCHARGE CURVE), Yuhao Lu etc. to invent, serial number 13/752,930, on January 29th, 2013 submits to,
Attorney docket SLA3265；(10) there is six cyano metal acid-salt negative electrodes, activated carbon anode and the super capacitor of aqueous electrolyte
Device (SUPERCAPACITOR WITH HEXACYANOMETALLATE CATHODE, ACTIVATED CARBON ANODE, AND
AQUEOUS ELECTROLYTE), Yuhao Lu etc. invent, serial number 13/603,322, within 2012, JIUYUE is submitted on the 4th, agency
People's Reference Number SLA3212；(11) improvement of the electric transmission of six cyano metal acid-salt electrodes of electrochemical applications it is used for
(IMPROVEMENT OF ELECTRON TRANSPORT IN HEXACYANOMETALLATE ELECTRODE FOR
ELECTROCHEMICAL APPLICATIONS), Yuhao Lu etc. invent, serial number 13/523,694, on June 14th, 2012
Submit to, attorney docket SLA3152；(12) there is six cyano metal acid-salt negative electrodes and the alkali metal ion of non-metallic anode and alkali
Earthmetal cations battery (ALKALI AND ALKALINE-EARTH ION BATTERIES WITH
HEXACYANOMETALLATE CATHODE AND NON-METAL ANODE), Yuhao Lu etc. invent, serial number 13/
On April 17th, 449,195,2012 submits to, attorney docket SLA3151；(13) for having six cyano metal acid-salt electrodes
Electrode forming method (the Electrode Forming Process for Metal-Ion Battery of metal ion battery
With Hexacyanometallate Electrode), Yuhao Lu etc. invent, serial number 13/432,993,2012 3
The moon 28 was submitted to, attorney docket SLA3146.
Industrial applicability
According to the present invention it is possible to provide the battery of preload, the anode of preload and relevant manufacturing process.
Claims (19)
1., for manufacturing the method that preload has the anode of consumption type metal, described method includes:
Offer select free carbon, can with the metal of metal (Me) electrochemically alloying, embed oxide, electro-chemical activity organic compound
Material (X) in the group of the combination composition of thing and material listed above；
Described metal (Me) is loaded to described material (X), and wherein Me selects free alkali metal, alkaline-earth metal and alkali metal and alkaline earth
The group of the combination composition of metal；
Formation is used for comprising M1yM2z(CN)n·mH2The anode of the preload comprising Me/X of the battery of O negative electrode；
Wherein M1 and M2 is transition metal；
Wherein y is less than or equal to 1；
Wherein z is less than or equal to 1；
Wherein n is less than or equal to 6；And
Wherein m is less than or equal to 20.
2. the method described in claim 1, it also includes:
Consume the described metal (Me) in the anode of described preload；With
Formation comprises the stable anode of described material (X).
3. the method described in claim 1, wherein,
Described metal (Me) loads to described material (X) include using the free physical mixed of choosing, chemical reaction and electrochemistry anti-
Technique in the group that should form.
4. the method described in claim 3, wherein,
Use chemical reaction that described metal (Me) loads to described material (X) to include with the reducing agent reduction X containing Me；And
The anode wherein forming described preload includes forming Me/X compound, and wherein Me Yu X has carried out chemical reaction.
5. the method described in claim 4, wherein,
The technique including selecting in the group of following composition with the reducing agent reduction X containing Me:
VO is reduced with n-BuLi2Form LirVO2, wherein 0 < r < 1；
With the NaH reduction MnO of tert-butyl group alkoxide activation in oxolane2Form NasMnO2, wherein 0 < s < 1；
TiO is reduced with NaH2Form NaTiO2；With
Sn mix particles is formed in the Na of fusing Na-Sn alloy.
6. the method described in claim 3, wherein,
Use physical mixed that described metal (Me) is loaded to described material (X) and be included in not causing between Me and X particle
Learn in the case of reacting in an inert atmosphere by Me and X particle mechanical mixture.
7. the method described in claim 6, wherein,
The technique including Me and X particle mechanical mixture selecting in the group of following composition:
In an ar atmosphere by ball milling mixing lithium powder and stannum particle, and
At a temperature of more than 100 degrees Celsius in industrial mixer mixed sodium particle and hard carbon powder and be then cooled to room
Temperature.
8. the method described in claim 3, wherein,
Use electrochemical reaction that described metal (Me) is loaded to described material (X) to include:
Formed the electrode of X and Me to electrode, both of which is inserted in electrolyte；
Carry out repeatedly discharge and recharge operation, wherein said charging operations use external power source generate from described electrode to described to electrode
Positive voltage current potential, and wherein said discharge operation is connected external loading at described electrode between to electrode；
Operate in response to described discharge and recharge, Me particle is inserted described material (X)；And
The anode wherein forming described preload includes forming Me/X compound, and wherein Me Yu X has carried out chemical reaction.
9. the method described in claim 8, wherein,
The electrode forming described X includes from hard carbon, stannum, antimony, Na2Ti3O7、Li4Ti5O12And Fe3O4Group in select X；And
Wherein form described Me includes selecting Me from the group being made up of lithium and sodium to electrode.
10. the method described in claim 3, wherein,
Use electrochemical reaction described metal (Me) is loaded to described material (X) be included in Me ionic conduction solution make Me and
X directly contacts；And
The anode wherein forming described preload includes forming Me/X compound, and wherein Me Yu X has carried out chemical reaction.
Method described in 11. claim 1, wherein,
Me selects free lithium (Li), sodium (Na), potassium (K), rubidium (Rb), caesium (Cs), calcium (Ca), terbium (Tb), strontium (Sr), barium (Ba), silver
(Ag), the group that aluminum (Al) and magnesium (Mg) form.
Method described in 12. claim 1, wherein,
M1 and M2 obtains independently of one another, M1 and M2 select in this manner free titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn),
The group that ferrum (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), calcium (Ca) and magnesium (Mg) form.
The anode of 13. 1 kinds of preloads, its preload has consumption type metal, the anode of described preload to comprise:
Conductive current collector；With
Cover the Me/X of described current collector, wherein X be select free carbon, can be with the metal of metal (Me) electrochemically alloying, embedding
Material in the group of the combination composition of oxide, electro-chemical activity organic compound and material listed above, and Me is for selecting
Metal in the group of the combination composition of free alkali metal, alkaline-earth metal and alkali and alkaline earth metal ions.
The anode of the preload described in 14. claim 13, wherein,
Me selects free lithium (Li), sodium (Na), potassium (K), rubidium (Rb), caesium (Cs), calcium (Ca), terbium (Tb), strontium (Sr), barium (Ba), silver
(Ag), the group that aluminum (Al) and magnesium (Mg) form.
The anode of the preload described in 15. claim 13, wherein,
The group of the following composition of Me/X choosing:
LirVO2, wherein 0 < r < 1；
NasMnO2, wherein 0 < s < 1；
Na-Sn alloy；
Lithium powder and the mixture of stannum particle；
Sodium particle and the mixture of hard carbon powder；
Hard carbon and the complex of lithium；
Hard carbon and the complex of sodium；
Li-Sn alloy；
Li-Sb alloy；
Na-Sb alloy；
Fe3O4Complex with Li；With
Fe3O4Complex with Na.
The battery of 16. 1 kinds of preloads, it has preload has the anode of consumption type metal, the battery of described preload to comprise:
Electrolyte；
The anode of preload, it comprises:
Conductive current collector；
Cover the Me/X of described current collector, wherein X be select free carbon, can be with the metal of metal (Me) electrochemically alloying, embedding
Material in the group of the combination composition of oxide, electro-chemical activity organic compound and material listed above, and Me is for selecting
Metal in the group of the combination composition of free alkali metal, alkaline-earth metal and alkali and alkaline earth metal ions；
Negative electrode, it comprises:
Conductive current collector；
Cover the M1 of described current collectoryM2z(CN)n·mH2O；
Wherein M1 and M2 is transition metal；
Wherein y is less than or equal to 1；
Wherein z is less than or equal to 1；
Wherein n is less than or equal to 6；
Wherein m is less than or equal to 20；With
Ion permeable membrane, described ion permeable membrane immerses in described electrolyte and is placed between described anode and described negative electrode.
The battery of the preload described in 17. claim 16, wherein,
Me selects free lithium (Li), sodium (Na), potassium (K), rubidium (Rb), caesium (Cs), calcium (Ca), terbium (Tb), strontium (Sr), barium (Ba), silver
(Ag), the group that aluminum (Al) and magnesium (Mg) form.
The battery of the preload described in 18. claim 16, wherein,
The group of the following composition of Me/X choosing:
LirVO2, wherein 0 < r < 1；
NasMnO2, wherein 0 < s < 1；
Na-Sn alloy；
Lithium powder and the mixture of stannum particle；
Sodium particle and the mixture of hard carbon powder；
Hard carbon and the complex of lithium；
Hard carbon and the complex of sodium；
Li-Sn alloy；
Li-Sb alloy；
Na-Sb alloy；
Fe3O4Complex with Li；With
Fe3O4Complex with Na.
The battery of the preload described in 19. claim 16, wherein,
M1 and M2 obtains independently of one another, M1 and M2 select in this manner free titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn),
The group that ferrum (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), calcium (Ca) and magnesium (Mg) form.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US14/198,663 US9537131B2 (en) | 2012-03-28 | 2014-03-06 | Battery anode with preloaded metals |
| US14/198,663 | 2014-03-06 | ||
| PCT/JP2015/001157 WO2015133139A1 (en) | 2014-03-06 | 2015-03-04 | Battery anode with preloaded metals |
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| CN106063013A true CN106063013A (en) | 2016-10-26 |
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| CN109309197A (en) * | 2017-07-26 | 2019-02-05 | 中能中科（天津）新能源科技有限公司 | Improve the method and its equipment of the yield of lithium carbon composite mass production |
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| CN113257583A (en) * | 2021-05-25 | 2021-08-13 | 江西理工大学 | Li3V2O5-carbon nanotube composite material, preparation method thereof and application thereof in lithium ion hybrid capacitor |
| CN113257583B (en) * | 2021-05-25 | 2023-02-14 | 江西理工大学 | Li 3 V 2 O 5 -carbon nanotube composite material, preparation method thereof and application thereof in lithium ion hybrid capacitor |
| CN113603133A (en) * | 2021-07-18 | 2021-11-05 | 武汉大学 | Sodium ion insertion type titanium oxide nanotube and preparation method thereof |
| CN113603133B (en) * | 2021-07-18 | 2022-04-15 | 武汉大学 | Sodium ion insertion type titanium oxide nanotube and preparation method thereof |
| CN116021007A (en) * | 2022-12-25 | 2023-04-28 | 复旦大学 | Sodium ion battery negative electrode pre-sodium agent and preparation method and application thereof |
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| WO2015133139A1 (en) | 2015-09-11 |
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