CN100423353C - Promoter for solid electrolyte film of lithium cell - Google Patents
Promoter for solid electrolyte film of lithium cell Download PDFInfo
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- CN100423353C CN100423353C CNB031567754A CN03156775A CN100423353C CN 100423353 C CN100423353 C CN 100423353C CN B031567754 A CNB031567754 A CN B031567754A CN 03156775 A CN03156775 A CN 03156775A CN 100423353 C CN100423353 C CN 100423353C
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- solid electrolyte
- electrode
- promoter
- electrolyte film
- lithium battery
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 44
- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 42
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 239000007772 electrode material Substances 0.000 claims abstract description 25
- 239000002184 metal Substances 0.000 claims abstract description 12
- 229910052802 copper Inorganic materials 0.000 claims abstract description 11
- 229910052751 metal Inorganic materials 0.000 claims abstract description 11
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 11
- 229910052737 gold Inorganic materials 0.000 claims abstract description 10
- 229910052741 iridium Inorganic materials 0.000 claims abstract description 10
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 10
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 10
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 10
- 229910052762 osmium Inorganic materials 0.000 claims abstract description 9
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 9
- 239000008187 granular material Substances 0.000 claims abstract description 8
- 229910052742 iron Inorganic materials 0.000 claims abstract description 8
- 229910052709 silver Inorganic materials 0.000 claims abstract description 8
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 7
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 4
- 239000002245 particle Substances 0.000 claims description 13
- 230000008021 deposition Effects 0.000 claims description 6
- 229910052776 Thorium Inorganic materials 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
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- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 229910052711 selenium Inorganic materials 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 229910052714 tellurium Inorganic materials 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 150000003624 transition metals Chemical class 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- 239000000956 alloy Substances 0.000 abstract description 6
- 229910052793 cadmium Inorganic materials 0.000 abstract description 6
- 229910052725 zinc Inorganic materials 0.000 abstract description 6
- 229910045601 alloy Inorganic materials 0.000 abstract description 4
- 150000001875 compounds Chemical class 0.000 abstract description 4
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- 238000002360 preparation method Methods 0.000 abstract description 4
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- 239000003795 chemical substances by application Substances 0.000 abstract 2
- 239000000463 material Substances 0.000 description 41
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- 230000005518 electrochemistry Effects 0.000 description 12
- 239000002904 solvent Substances 0.000 description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 11
- 229910052799 carbon Inorganic materials 0.000 description 9
- 239000011324 bead Substances 0.000 description 8
- 238000006253 efflorescence Methods 0.000 description 8
- 206010037844 rash Diseases 0.000 description 8
- 239000010949 copper Substances 0.000 description 7
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 7
- 229910000733 Li alloy Inorganic materials 0.000 description 6
- 230000008859 change Effects 0.000 description 6
- 125000004122 cyclic group Chemical group 0.000 description 6
- 238000000354 decomposition reaction Methods 0.000 description 6
- 238000005087 graphitization Methods 0.000 description 6
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- 239000011149 active material Substances 0.000 description 5
- 239000003610 charcoal Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000000151 deposition Methods 0.000 description 5
- 238000007599 discharging Methods 0.000 description 5
- 239000002086 nanomaterial Substances 0.000 description 5
- 229910052718 tin Inorganic materials 0.000 description 5
- -1 transition metal nitride Chemical class 0.000 description 5
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 239000001989 lithium alloy Substances 0.000 description 4
- 229910000498 pewter Inorganic materials 0.000 description 4
- 239000010957 pewter Substances 0.000 description 4
- 238000005240 physical vapour deposition Methods 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 3
- 238000002955 isolation Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000002931 mesocarbon microbead Substances 0.000 description 3
- 230000002441 reversible effect Effects 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
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- 239000011258 core-shell material Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 1
- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 0.000 description 1
- 229910001316 Ag alloy Inorganic materials 0.000 description 1
- 229910017609 Ag0.4Zn0.55O0.05 Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910017653 Cu0.4Th0.2Sn0.4 Inorganic materials 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229910009439 Sn0.44Sb0.16Cu0.4 Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- RRKGBEPNZRCDAP-UHFFFAOYSA-N [C].[Ag] Chemical compound [C].[Ag] RRKGBEPNZRCDAP-UHFFFAOYSA-N 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
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- 239000000295 fuel oil Substances 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910003480 inorganic solid Inorganic materials 0.000 description 1
- 238000006713 insertion reaction Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 229910021450 lithium metal oxide Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
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- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Images
Classifications
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- Y02P70/54—
Abstract
The present invention relates to an accelerating agent of a solid compound film used for a lithium battery, which is a nanometer metal selected from Ag, Cu, Au, Zn, Cd, Fe, Co, Ni, Ru, Rh, Pd, Pt, Ir, Os or Al, or is a nanometer alloy with expression of M<x1><1>M<x2><2>... M<xn><n>, wherein M<1>, M<2>... M<n> represent different elements which are selected from main group elements, such as Li, etc., or transition metal elements, such as Ag, etc., and at least contain one of Ag, Cu, Au, Zn, Cd, Hg, Fe, Co, Ni, Ru, Rh, Pd, pt, Ir, Os or Al, and the average size of granules is from 0.3 to 250 nm. The accelerating agent is deposited at an electrode surface to form a solid electrolyte membrane with certain elasticity on the electrode surface of a secondary lithium battery. Thereby, the cycle life of electrode materials is increased, the battery has good electrochemical circularity and high-current performance, and the present invention can lower electrode preparation costs and meet the requirement of large-power charge and discharge batteries for portable electronic devices, electric automobiles, etc. in the future.
Description
Technical field
The present invention relates to a kind of promoter and uses thereof and using method of the solid electrolyte film that is used for lithium battery, specifically relate to a kind of promoter that is used for forming organic/inorganic solid electrolyte film on the electrode material granules of serondary lithium battery surface, and uses thereof and using method.
Technical background
Thinking makes people to carrying out new planning the future of fuel-engined vehicle to the concern of environment with to energy starved.With the high energy serondary lithium battery is the electric automobile of power and be that the hybrid-electric car of power has been subjected to increasing attention with fuel oil and battery simultaneously, and this has proposed high-power requirement to secondary lithium battery.Because the surperficial solid electrolyte film that the secondary lithium battery cathode material surface forms in discharge process has very big influence to the performance of electrode material, it is an electronic isolation, this has just increased the internal resistance of battery, greatly limited the high-rate performance of battery, power density is difficult to be further enhanced, how to form flexible stable solid electrolyte film at electrode surface, how improving the conductivity of solid electrolyte film, is to improve particularly negative material cycle life of at present used electrode material thereby reduce the material surface resistance reduction internal resistance of cell, improve the key of the high-power performance of lithium ion battery.
The electrolyte that serondary lithium battery is commonly used is carbonates, the ethers nonaqueous solvents.Because the operating voltage of serondary lithium battery is higher, can form reducing environment at negative pole during operate as normal near the lithium metal reduction potential, thereby as the carbonates of electrolyte, nonaqueous solventss such as ethers are at this spread of voltage, solvent molecule will obtain electronics and decompose in negative terminal surface, and its reduction decomposition product just forms solid electrolyte film in the electrode surface deposition.This layer solid electrolyte film is electronic isolation, covers electrode material surface if it can be fine and close, just can effectively stop the carbonates material to obtain electronics and further be reduced decomposition from electrode; This layer solid electrolyte film has very high ionic conductance again simultaneously, allows ion to pass through with very high speed, finishes the electrochemistry embedding and takes off the embedding process.But, understand will as Feng in electrochemistry, 137 volumes, 2009 pages, described in nineteen ninety, this layer dielectric film is rigidity, if electrode material experiences bigger change in volume in charge and discharge process, this layer dielectric film just might come off, the exposed inevitable requirement of new electrode surface forms new surperficial solid electrolyte film, further electrolyte decomposition and form solid electrolyte film and must cause the capacity attenuation of electrode material in cyclic process, this irreversible capacitance loss has damaged the performance of material.
As the secondary lithium battery cathode material, comparatively general have material with carbon element, but embedding lithium metal or alloy, transition metal oxide, but embedding lithium metal oxide, transition metal nitride etc.
Material with carbon element comprises graphitized material and non-graphitized material.Graphitization class material with carbon element wherein, under low-voltage, exist organic solvent to enter the common insertion reaction of graphite flake layer, it is a competitive reaction that this reduction decomposition with electrolyte in charge and discharge process forms solid electrolyte film, and the electrode that causes peels off and inefficacy can't be used this class material in actual battery because solvent embeds altogether.In order to address this problem, mainly be at present by in electrolyte, adding organic or inorganic additive, making electrode surface when being higher than solvent embedding current potential, form the solid electrolyte layer that does not allow solvent only to allow lithium ion to pass through and come; Or use and to be decomposed to form the dominant organic solvent of solid electrolyte film reaction, as vinyl carbonate etc.But these additives or the solvent that forms solid electrolyte film easily because the solid electrolyte film that the surface forms is an electronic isolation, can make the dynamic behavior variation of material, the high-rate performance variation when solving the problem that solvent embeds altogether.In addition, because the employed electrolyte of serondary lithium battery must dewater in strictness, substance can cause the electrolyte complex manufacturingization in electrolyte, has improved production cost of cells.Moreover generally speaking, the cryogenic property of solvent that is decomposed to form solid electrolyte film easily is generally relatively poor, and ionic conductance is low, and this has just limited the operating temperature range of battery.
But embedding lithium alloy or metal are another kind of serondary lithium battery negative materials, and they generally have very high embedding lithium capacity.But because there is huge change in volume in this material in the removal lithium embedded process, cause material efflorescence gradually in cyclic process, this efflorescence meeting comes off electrode active material gradually from electrode surface on the one hand, make that available active material is fewer and feweri, simultaneously, these active materials that come off can cause the positive and negative electrode internal short-circuit, cause battery heating even blast, cause safety problem; And on the other hand, because the solid electrolyte film that material surface forms is an electric insulation, the insulated solid electrolyte film in the edge of particle surrounds after the efflorescence, even without coming off from electrode surface, also can lose and electrically contact, become " dead capacity ", cause capacity attenuation in the cyclic process with electrode; Moreover the surperficial solid electrolyte film of rigidity is easy to come off in cyclic process, and new solid electrolyte film constantly forms and causes further capacity attenuation.
But use nanometer embedding lithium alloy as the serondary lithium battery negative material, because absolute volume changes little in charge and discharge process, can not produce the efflorescence of material in charge and discharge process, thereby cause the problem of capacity attenuation, the electrochemistry embedding lithium capacity of nano material can not diminish yet simultaneously.Use at present the method for nano material to have two kinds, a kind of is the invertibity that improves material by the nanometer embedding lithium alloy that uses polymer overmold, can will as Bock peace etc. in electrochemistry, and 128 volumes, 725 pages, 1981 are described.Another is to utilize the bulky grain material with carbon element as matrix, and the electrochemistry that Nanoalloy suppresses material on the surperficial pinning is reunited, can will as Li Hong etc. in electrochemistry, and 148 volumes, 915 pages, described in calendar year 2001.These methods use the pinning of polymer overmold or large particle surface that the contact probability between the nano material is reduced, and have suppressed the electrochemistry of nano material and have reunited.But change because material can experience bigger relative volume equally in charge and discharge process, the solid electrolyte film of material surface rigidity still can come off; But and to obtain homogeneous polymer/nanometer embedding lithium alloy composite material, the C-base composte material technology more complicated of Nanoalloy particle pinning has increased the material preparation cost; And when using polymer actual weight specific capacity and volume and capacity ratio are all reduced, and to obtain cyclicity preferably the alloy content of the C-base composte material of Nanoalloy pinning generally be no more than 30%, this makes the embedding lithium ability of alloy well not be applied.
Summary of the invention
The objective of the invention is to overcome solid electrolyte film that prior art forms exists easily to peel off and causes electrode material to lose efficacy, add additive and easily cause electrode material dynamic behavior and high-rate performance variation, and raising production cost of cells, defectives such as limit battery operating temperature range, thereby providing a kind of helps formation neither can make electrode material dynamic behavior and high-rate performance variation, can not improve the battery manufacturing cost again, the restraint of labour temperature range, the solid electrolyte film that can stop the electrolyte reduction decomposition, and can solve electrode and peel off promoter with the solid electrolyte film that is used for lithium battery of Problem of Failure.
Another object of the present invention is to provide a kind of purposes of promoter of the described solid composite membrane that is used for lithium battery.
A further object of the present invention is to provide a kind of using method of promoter of the described solid composite membrane that is used for lithium battery.
The objective of the invention is to realize by the following technical solutions:
The invention provides a kind of promoter that is used for the solid composite membrane of lithium battery, it is characterized in that, this promoter is nano metal or the Nanoalloy at electrode or electrode material granules surface deposition.
Described nano metal is to be selected from a kind of among Ag, Cu, Au, Zn, Cd, Fe, Co, Ni, Ru, Rh, Pd, Pt, Ir, Os or the Al.
The expression formula of described Nanoalloy is M
1 X1M
2 X2M
n Xn, M wherein
1, M
2M
nRepresent different elements, be selected from the Li in the major element, Mg, B, Al, Si, Ge, Sn, Pb, Sb, S, Se, Te, or the Ag of transition metal, Cu, Au, Zn, Cd, Ti, V, Mn, Fe, Co, Ni, Th, Hg, Al, Fe, Co, Ni, Ru, Rh, Pd, Pt, Ir, Os, and contain Ag at least, Cu, Au, Zn, Cd, Hg, Fe, Co, Ni, Ru, Rh, Pd, Pt, Ir, a kind of among Os or the Al, Ag, Cu, Au, Zn, Cd, Hg, Fe, Co, Ni, Ru, Rh, Pd, Pt, Ir, 16 kinds of elements of Os or Al in expression formula shared molar percentage and be not less than 30%; Subscript x1, x2 ... xn represents the molar percentage of different element atoms, and x1+x2+ ... + xn=1.
The average-size of described nano metal or Nanoalloy particle is 0.3nm～10um.
Described Nanoalloy is Ag
0.67Te
0.33, Ag
0.75Hg
0.25, Ag
0.75Sb
0.25, Ag
0.50Zn
0.50, Au
0.9Hg
0.1, Au
0.73Mn
0.27, Cu
0.67S
0.33, Cu
0.67Se
0.33, Cu
0.4Th
0.2Sn
0.4, Sn
0.50Ag
0.50, Ag
0.88Sb
0.12, Sn
0.44Sb
0.16Cu
0.4, Ag
0.4Zn
0.55O
0.05, Pt
0.5Rh
0.5, Fe
0.5Ni
0.5, Co
0.5Ni
0.5
The invention provides a kind of described promoter conduct that is used for the solid electrolyte film of lithium battery forms the promoter of solid electrolyte film at the electrode surface of serondary lithium battery purposes.
The invention provides a kind of using method of promoter of the described solid electrolyte film that is used for lithium battery, it is characterized in that, during use, with the nano metal of described promoter or Nanoalloy particle at electrode or electrode material granules surface deposition.
The promoter that is used for the solid electrolyte film of lithium battery provided by the invention, compared with the prior art, tangible advantage is arranged: by adding this promoter, can in the electrochemistry cyclic process, form the uniform network structure that is similar to conducting polymer, this strata compound film original position in charge and discharge process forms, have necessarily flexible, can the bigger change in volume of sustaining electrode material and do not come off, thereby improve the cycle life of electrode material, solve the electron conduction ability and the stable inadequately problem of original solid electrolyte film, and stoped the electrochemistry of nano material to be reunited; This strata compound film can be used as solid electrolyte film again, stops the reduction decomposition of solvent, and stops because solvent embeds the capacitance loss that causes altogether; This strata compound film also has very high electronic conductance, can obviously reduce contact resistance between the electrode material, thereby makes battery have good electrochemistry cyclicity and high-rate performance; Because the complete original position of this layer solid electrolyte film forms, the homogeneity of resulting material is good, and preparation greatly reduces the electrode preparation cost easily; Can satisfy following mancarried electronic aid and electric automobile, hybrid-electric car etc. to the high-power requirement that discharges and recharges of battery.
Description of drawings
Fig. 1 is the X-ray diffractogram of the composite material that forms of charcoal bead mutually in the middle of nano-Ag particles and the graphitization in the embodiment of the invention 5;
Fig. 2 is the stereoscan photograph of the composite material that forms of charcoal bead mutually in the middle of nano-Ag particles and the graphitization in the embodiment of the invention 5;
Fig. 3 is phase charcoal bead nano surface particle constituency X ray energy dispersion analysis in the middle of the graphitization in the embodiment of the invention 5;
Fig. 4 be with in the middle of nano-Ag particles in the embodiment of the invention 5 and the graphitization mutually the composite material that forms of charcoal bead in lithium button simulated battery, be the stereoscan photograph of carbon bead electrode during through low discharging current to 0.0 volt in the electrolyte of solvent with the propylene carbonate;
Fig. 5 be with in the comparative example 1 of the present invention in the middle of the graphitization phase charcoal bead in lithium button simulated battery, be the stereoscan photograph of carbon bead electrode during through low discharging current to 0.0 volt in the electrolyte of solvent with the propylene carbonate;
Fig. 6 is the structural representation of lithium button simulated battery in the embodiment of the invention 1, wherein stainless steel sealing nut and electrode leading-out end 1, polytetrafluoroethylene nut 2, electrode copper collector 3, the work electrode 4 that the nanometer Ag alloy/spherical pyrolyzed hard carbon composite material is an active material, the porous polypropylene barrier film
(soaking through electrolyte) 5, thick 0.4mm, area are 1cm
2Metal lithium sheet to electrode 6;
Fig. 7 is for adopting the embodiment of the invention 1 (curve 1), and active material is as the charging and discharging curve of the lithium button simulated battery of negative active core-shell material in the comparative example 1 (curve 2).
Embodiment
The present invention is further illustrated below by embodiment.
The nano-Ag particles that with granularity is 0.3nm is in the electrode surface deposition that with the tin pewter is electrode material: the method for utilizing physical vapour deposition (PVD), in the physical vapour deposition (PVD) stove that vacuumizes, add evaporation source Ag, on the matrix of tin pewter electrode slice, sedimentation time is 2 minutes.
This surface deposition there is the electrode slice of nanometer metallic silver dried 12 hours down at 150 ℃.It is 1cm that oven dry back composite material is cut to area
2Thin rounded flakes investigate its chemical property as combination electrode as the serondary lithium battery negative active core-shell material, adopt one the experiment button cell study.The Experimental cell structure as shown in Figure 6, electrolyte is the lithium hexafluoro phosphate (LiPF of 1 mol
6) be dissolved in the solution of propylene carbonate, after stainless steel sealing nut 1, polytetrafluoroethylene nut 2, stainless steel spring sheet 3, work electrode 4, porous polypropylene barrier film 5 dryings, in the argon filling glove box by the Experimental cell that is assembled into shown in Figure 6.Experimental cell is tested by being subjected to computer-controlled auto charge and discharge instrument to carry out charge and discharge cycles.Current density is 0.1mA/cm
2, the charging cut-ff voltage is 2.0V, discharge cut-off voltage is 0.00V.The data that record are listed in table 1.
According to the method among the embodiment 1, difference is formed and the promoter of granularity deposits to electrode surface, and the character of test electrode, the data that record are listed in table 1.
Table, 1 is made up of and the promoter of granularity deposits to the character of surperficial electrode difference
The composite material that obtains of material is done X-ray diffraction as shown in Figure 1 among the embodiment 5, and the gained material does not have other material except that MCMB and Nano Silver as can be seen.Fig. 2 is the stereoscan photograph of gained composite material, and nano-Ag particles size 8 nanometers as can be seen are on 5 microns the carbon bead attached to average-size.Its surperficial constituency X ray energy dispersion analysis result shows that this material is the carbon silver composite material as shown in Figure 3.The circulate sem photograph on 20 all rear electrodes surfaces of material is seen Fig. 4, and after material granule circulated in propylene carbonate electrolyte as can be seen, carbon granule was kept perfectly, not efflorescence.The charging and discharging curve of material is referring to the curve 1 of Fig. 7, and the cyclicity of material is good.Comparative example 1～4,
According to the method among the embodiment 1, the character of the electrode of promoter is not used in test, and the data that record are listed in table 2.
Table 2, do not use the character of the electrode of promoter
| Comparative example | Electrode material | Capability retention after 20 weeks | High- |
20 all circulation rear |
| 1 | Tin pewter | 25％ | Difference | The material efflorescence is serious, and electrode active material comes off |
| 2 | |
20％ | Difference | Electrode active material comes off |
| 3 | The |
40％ | Difference | Electrode active material comes off |
| 4 | MCMB | 5％ | Difference | Material structure destroys, and electrode active material comes off |
Electrode is seen Fig. 5 through the sem photograph on 20 all circulation rear electrodes surfaces in the comparative example 4, the complete efflorescence of carbon granule as can be seen, and its charging and discharging curve is seen curve 2 among Fig. 7, the material cyclicity is poor.
By the result of table 1 and table 2 as can be seen, do not add nano metal or Nanoalloy form promoter as surperficial solid electrolyte film graphite-based electrode material propylene carbonate (PC) for the electrolyte of base in matching poor, almost do not have reversible capacity; And but for materials such as alloyed metal (AM) or alloys, owing to there is great change in volume in charge and discharge process, the electrode powder of detached is serious, thereby the very fast decline of reversible capacity; And for other materials such as Nanoalloys, same owing to have change in volume in the electrochemistry cyclic process, making in the material in the insulating properties of the solid electrolyte film of the active material particle spontaneous formation in surface simultaneously has " dead capacity " to form, and cyclicity is poor.These phenomenons obtain obvious suppression after adding surperficial solid electrolyte film promoter, as graphite-like negative materials such as MCMB can be in not adding the PC base electrolyte of any additives Reversible Cycle, but the electrochemistry cyclicity of other embedding lithium metal or alloy also is significantly improved, not efflorescence of electrode material does not come off.
Claims (4)
1. a promoter that is used for the solid electrolyte film of lithium battery is characterized in that, this promoter is nano metal or the Nanoalloy at electrode or electrode material granules surface deposition;
Described nano metal is to be selected from a kind of among Ag, Cu, Au, Fe, Co, Ni, Ru, Rh, Pd, Pt, Ir, Os or the Al;
The expression formula of described Nanoalloy is M
1 X1M
2 X2M
n Xn, M wherein
1, M
2M
nRepresent different elements, be selected from Li, Mg, B, Al, Si, Ge, Pb, S, Se, Te in the major element, or the Ag in the transition metal, Cu, Au, Ti, V, Mn, Fe, Co, Ni, Th, Ru, Rh, Pd, Pt, Ir, Os, and contain a kind of among Ag, Cu, Au, Fe, Co, Ni, Ru, Rh, Pd, Pt, Ir, Os or the Al at least, these 13 kinds of elements of Ag, Cu, Au, Fe, Co, Ni, Ru, Rh, Pd, Pt, Ir, Os and Al in expression formula shared molar percentage and be not less than 30%; Subscript x1, x2 ... xn represents the molar percentage of different element atoms, and x1+x2+ ... + xn=1.
2. by the described promoter that is used for the solid electrolyte film of lithium battery of claim 1, it is characterized in that the average-size of described nano metal or Nanoalloy particle is 0.3nm～10 μ m.
3. by the described promoter that is used for the solid electrolyte film of lithium battery of claim 1, it is characterized in that described Nanoalloy is Ag
0.67Te
0.33, Au
0.73Mn
0.27, Cu
0.67S
0.33, Cu
0.67Se
0.33, Pt
0.5Rh
0.5, Fe
0.5Ni
0.5Or Co
0.5Ni
0.5
One kind by the promoter of the described solid electrolyte film that is used for lithium battery of claim 1 as the purposes that forms the promoter of solid electrolyte film at the electrode surface of serondary lithium battery.
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| DE102014207531A1 (en) | 2014-04-22 | 2015-10-22 | Bayerische Motoren Werke Aktiengesellschaft | Galvanic element with solid-state cell stack |
| CN109728281B (en) * | 2018-12-31 | 2021-10-12 | 青岛农业大学 | Preparation method of surface modified SiOx electrode material |
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|---|---|---|---|---|
| CN1327275A (en) * | 2000-06-06 | 2001-12-19 | 中国科学院物理研究所 | Secondary lithium cell having negative pole of carbon with deposited nanometer alloy on its surface |
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