CN105702919A - Lithium battery electrode preparation method including polymer material with stable interface and application of lithium battery electrode in solid lithium battery - Google Patents
Lithium battery electrode preparation method including polymer material with stable interface and application of lithium battery electrode in solid lithium battery Download PDFInfo
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- CN105702919A CN105702919A CN201610208378.XA CN201610208378A CN105702919A CN 105702919 A CN105702919 A CN 105702919A CN 201610208378 A CN201610208378 A CN 201610208378A CN 105702919 A CN105702919 A CN 105702919A
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 111
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 96
- 239000007787 solid Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000002861 polymer material Substances 0.000 title abstract description 13
- 229920001577 copolymer Polymers 0.000 claims abstract description 36
- 229920000642 polymer Polymers 0.000 claims abstract description 27
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000007772 electrode material Substances 0.000 claims abstract description 9
- 239000000178 monomer Substances 0.000 claims abstract description 6
- 239000000463 material Substances 0.000 claims description 55
- 239000003792 electrolyte Substances 0.000 claims description 33
- 239000011230 binding agent Substances 0.000 claims description 23
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 17
- 239000010439 graphite Substances 0.000 claims description 17
- 229910002804 graphite Inorganic materials 0.000 claims description 17
- 238000001291 vacuum drying Methods 0.000 claims description 16
- 229910052493 LiFePO4 Inorganic materials 0.000 claims description 12
- 238000006116 polymerization reaction Methods 0.000 claims description 12
- 230000006641 stabilisation Effects 0.000 claims description 11
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 10
- 239000010406 cathode material Substances 0.000 claims description 9
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 8
- 229910032387 LiCoO2 Inorganic materials 0.000 claims description 8
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 claims description 8
- 239000011149 active material Substances 0.000 claims description 8
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 8
- 239000003999 initiator Substances 0.000 claims description 8
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 6
- 229910011849 LiFe0.2Mn0.8PO4 Inorganic materials 0.000 claims description 6
- 229910002099 LiNi0.5Mn1.5O4 Inorganic materials 0.000 claims description 6
- FXPHJTKVWZVEGA-UHFFFAOYSA-N ethenyl hydrogen carbonate Chemical compound OC(=O)OC=C FXPHJTKVWZVEGA-UHFFFAOYSA-N 0.000 claims description 6
- UFLFSNVZQRNKOX-UHFFFAOYSA-N carbonic acid;ethenyl acetate Chemical compound OC(O)=O.CC(=O)OC=C UFLFSNVZQRNKOX-UHFFFAOYSA-N 0.000 claims description 5
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 claims description 4
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 239000000956 alloy Substances 0.000 claims description 4
- 229910003481 amorphous carbon Inorganic materials 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 238000010276 construction Methods 0.000 claims description 4
- AWKHTBXFNVGFRX-UHFFFAOYSA-K iron(2+);manganese(2+);phosphate Chemical compound [Mn+2].[Fe+2].[O-]P([O-])([O-])=O AWKHTBXFNVGFRX-UHFFFAOYSA-K 0.000 claims description 4
- 239000005543 nano-size silicon particle Substances 0.000 claims description 4
- -1 nickel cobalt aluminum Chemical compound 0.000 claims description 4
- 229910001453 nickel ion Inorganic materials 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- WYGWHHGCAGTUCH-UHFFFAOYSA-N 2-[(2-cyano-4-methylpentan-2-yl)diazenyl]-2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)C WYGWHHGCAGTUCH-UHFFFAOYSA-N 0.000 claims description 2
- 230000000977 initiatory effect Effects 0.000 claims description 2
- 239000007784 solid electrolyte Substances 0.000 abstract description 14
- 210000001787 dendrite Anatomy 0.000 abstract description 6
- 238000000354 decomposition reaction Methods 0.000 abstract description 4
- 230000006378 damage Effects 0.000 abstract description 3
- 238000012662 bulk polymerization Methods 0.000 abstract 1
- 239000013039 cover film Substances 0.000 abstract 1
- 150000003254 radicals Chemical class 0.000 abstract 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 31
- 229910001416 lithium ion Inorganic materials 0.000 description 31
- 229920001756 Polyvinyl chloride acetate Polymers 0.000 description 30
- 239000000243 solution Substances 0.000 description 27
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 16
- 239000002904 solvent Substances 0.000 description 14
- 210000004027 cell Anatomy 0.000 description 12
- 238000005253 cladding Methods 0.000 description 10
- 229910052786 argon Inorganic materials 0.000 description 8
- 238000011065 in-situ storage Methods 0.000 description 8
- 150000002500 ions Chemical class 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 230000008569 process Effects 0.000 description 7
- 229910013188 LiBOB Inorganic materials 0.000 description 6
- 229910010710 LiFePO Inorganic materials 0.000 description 5
- 239000011572 manganese Substances 0.000 description 5
- 239000011259 mixed solution Substances 0.000 description 5
- 229910012820 LiCoO Inorganic materials 0.000 description 4
- 229910018060 Ni-Co-Mn Inorganic materials 0.000 description 4
- 229910018209 Ni—Co—Mn Inorganic materials 0.000 description 4
- 230000004888 barrier function Effects 0.000 description 4
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 4
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 4
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- 230000002427 irreversible effect Effects 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 3
- 230000010287 polarization Effects 0.000 description 3
- 229910013716 LiNi Inorganic materials 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- XSAOIFHNXYIRGG-UHFFFAOYSA-M lithium;prop-2-enoate Chemical compound [Li+].[O-]C(=O)C=C XSAOIFHNXYIRGG-UHFFFAOYSA-M 0.000 description 2
- 229940117958 vinyl acetate Drugs 0.000 description 2
- 229920001651 Cyanoacrylate Polymers 0.000 description 1
- 229910013075 LiBF Inorganic materials 0.000 description 1
- MWCLLHOVUTZFKS-UHFFFAOYSA-N Methyl cyanoacrylate Chemical compound COC(=O)C(=C)C#N MWCLLHOVUTZFKS-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000006253 efflorescence Methods 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 206010037844 rash Diseases 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
- H01M4/621—Binders
- H01M4/622—Binders being polymers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a lithium battery electrode preparation method including polymer material with a stable interface and the application of a lithium battery electrode in a solid lithium battery. The preparation method is characterized in that the polymer material with the stable interface is poly-vinylene carbonate (PVCA) or copolymers thereof. The free radical triggers the monomer to perform mass polymerization to obtain a polymer, the polymer material with the stable interface can form a cover film on the surface of the electrode, thus destruction on the electrode material and decomposition of the solid electrolyte on the surfaces of the positive and negative electrodes can be effectively restrained. Meanwhile, the polymer material can form a stable protection layer on the surface of lithium metal to inhibit the growth of the lithium dendrites, thus the cycle performance of the solid lithium battery is improved. The invention also provides a preparation method of the electrochemical stable polymer material, and the solid lithium battery assembled by using the polymer material.
Description
Technical field
The present invention relates to battery technology, polymerized thylene carbonate vinyl acetate or its copolymer are as the preparation method of electrode of lithium cell interface stability polymeric material specifically, and the application that electrode interface stabilisation of polymeric materials is in solid state lithium battery。
Background technology
Lithium ion battery refers to the electrochemical appliance carrying out embedding storage and the release realizing energy with deviating from by lithium ion between both positive and negative polarity。Lithium ion battery is actually a kind of lithium ion concentration cell, and during charging, lithium ion is deviate from from positive pole, embeds negative pole through electrolyte。Now, positive pole is in lean lithium state due to deviating from of lithium ion, and negative pole is in rich lithium state due to the embedding of lithium ion。The positive electrode deviating from lithium ion discharges electronics to external circuit, and the negative material embedding lithium ion receives the electronics of external circuit, and then guarantees the charge balance of both positive and negative polarity。During electric discharge, this process is then contrary。Positive pole embeds lithium ion and receives electronics, and negative pole deviates from lithium ion and release electronics simultaneously。Ideal situation, lithium ion embed with deviate from the crystal structure that will not destroy both positive and negative polarity, the charge and discharge process completely reversibility of lithium ion battery。, in reality, lithium ion battery understands the decay of guiding discharge capacity along with the increase of access times。This is because: 1) repeated charge can make electrode material surface active area reduce, and polarization increases, and electrode material structure changes；2) electrolytical decomposition can passivation on electrode with electrolyte interface；3) obstruction of barrier film or destruction。
For improving the cycle performance of lithium ion battery, carry out coating modification at electrode surface and achieve certain success to improve electrode interface stability。CN105283998A discloses a kind of method at electrode surface synthesis of solid electrolyte interface, and this patent makes electrode material have superior discharge rate capacity and charge and discharge cycles stability by being coated with one layer of solid electrolyte interface at electrode surface。CN103606699A discloses a kind of lithium ion battery, this lithium ion battery positive and negative plate surface-coated one layer of polymeric carrier, the efflorescence of electrode material can be significantly inhibited, burst apart and reunite such that it is able to the cycle performance and the holding electrode that improve electrode material are stable。CN105226289A discloses a kind of based lithium-ion battery positive plate and its preparation method and application, and organic granular fully swelling in this coating material can be effectively improved the active force between positive electrode and organic barrier film, improves the interfacial characteristics between positive pole and barrier film。Although making various effort, scientific research personnel successfully cannot prepare interface stability material and with this in a large number to improve the cyclical stability of solid lithium battery, coulombic efficiency and high rate performance。Compared with these patents, a kind of polymerized thylene carbonate vinyl ester full solid state polymer material that the application provides acts not only as electrode of lithium cell interface stability material and improves the cycle performance of solid state lithium battery, the lithium ion transfer rate in electrode interior can also be improved, and then improve the high rate performance of solid state lithium battery。Lithium battery both positive and negative polarity interface stability polymerized thylene carbonate vinyl ester full solid state polymer material can improve electrode of lithium cell and electrolytical interface stability, and then reduces the polarization phenomena in charge and discharge process。Electrode interface stablizes all solid state material can also avoid directly contacting of electrode and electrolyte, it is suppressed that the decomposition of electrolyte and the irreversible loss of capacity that causes。In addition, electrode interface is stablized full solid state polymer material and can also be formed layer protecting film on metallic lithium surface, it is suppressed that the generation of Li dendrite so that it is the solid lithium battery of assembling has superior cycle performance。The performance of these advantages and other excellences that the application electrode interface stablizes full solid state polymer material is shown in the accompanying drawing of the application, describes and talk about part。
Summary of the invention
It is an object of the invention to provide a kind of electrode of lithium cell preparation method comprising interface stability polymeric material and the application in solid state lithium battery。
The technical solution used in the present invention is for achieving the above object:
A kind of electrode of lithium cell preparation method comprising interface stability polymeric material, interface stability polymer is polymerized thylene carbonate vinyl acetate or its copolymer, and electrode preparation method key step is as follows:
1) vinylene carbonate or the multi-component copolymer monomer containing vinylene carbonate carry out polymerisation in bulk under the initiation of initiator and obtain electrode interface stabilisation of polymeric materials；
2) being dissolved in DMF (DMF) by electrode interface stabilisation of polymeric materials, obtain polymer solution, wherein electrode of lithium cell interface stability polymeric material mass fraction in a polymer solution is 2%-50%；
3) preparing anode for lithium battery pole piece and cathode pole piece with electrode of lithium cell interface stability polymeric material for binding agent, binding agent mass fraction in electrode material is 5%-30%；
4) prepared electrode plates or metal lithium electrode immersing taking-up after 1-60 minute in above-mentioned polymer solution, vacuum drying obtains solid state lithium battery electrode。
Described polymeric material all contains vinylene carbonate (VCA) chain link, and the structure of vinylene carbonate (VCA) chain link is as follows:
；
Described and vinylene carbonate copolymerization monomer includes the one in maleic anhydride (MAH), pi-allyl-1,3-sultones (PST), vinylacetate (VA), acrylonitrile (AN), acrylamide (AM), cyanoacrylate (ECA), Lithium acrylate (LiMAA), methyl methacrylate (MMA)；
The structure of described electrode of lithium cell interface stability polymeric material is as follows:
；；；；；；；；；
Wherein m is the degree of polymerization of vinylene carbonate construction unit, and span is 2-105；N is the degree of polymerization of comonomer, and span is 0-105。
To vinylene carbonate or containing in vinylene carbonate multi-component copolymer monomer add mass fraction be the initiator of 0.1%-1.0%；The solution adding initiator is placed in 40-80oIt is polymerized 2-24 hour under C, namely obtains polymerized thylene carbonate vinyl acetate or polymerized thylene carbonate vinyl ester copolymers；In copolymer, vinylene carbonate construction unit mass fraction in the copolymer is 10%-99%。
Described initiator is the one in azodiisobutyronitrile (AIBN), 2,2'-Azobis(2,4-dimethylvaleronitrile) (ABVN), azo-bis-iso-dimethyl (AIBME), benzoyl peroxide (BPO), the benzoyl peroxide tert-butyl ester (TBPB), methyl ethyl ketone peroxide (MEKPO)。
Described electrode of lithium cell interface stability polymeric material thickness on anode pole piece, cathode pole piece or lithium metal is 0.05-10 μm。
The active material of described positive pole includes LiFePO4 (LiFePO4), iron manganese phosphate for lithium (LiFe0.2Mn0.8PO4), cobalt acid lithium (LiCoO2), LiMn2O4 (LiMn2O4), nickel ion doped (LiNi0.5Mn1.5O4), nickel cobalt aluminum or nickel-cobalt-manganese ternary material electrodes；
The active material of described negative pole includes lithium metal, graphite, amorphous carbon, carbonaceous mesophase spherules, silicon-carbon cathode, tin base cathode material, nano silicon-based negative material, lithium titanate or alloy material。
The application in solid state lithium battery of the electrode of lithium cell of prepared by preparation method described above comprise interface stability polymeric material。
A kind of solid state lithium battery, including positive pole, negative pole, electrolyte between both positive and negative polarity, it is characterized in that: positive pole and negative pole are the lithium battery anode comprising interface stability polymeric material and negative pole prepared according to preparation method described above, electrolyte between both positive and negative polarity is polymerized thylene carbonate vinyl ester electrolyte
The active material of described positive pole includes LiFePO4 (LiFePO4), iron manganese phosphate for lithium (LiFe0.2Mn0.8PO4), cobalt acid lithium (LiCoO2), LiMn2O4 (LiMn2O4), nickel ion doped (LiNi0.5Mn1.5O4), nickel cobalt aluminum or nickel-cobalt-manganese ternary material electrodes；
The active material of described negative pole includes lithium metal, graphite, amorphous carbon, carbonaceous mesophase spherules, silicon-carbon cathode, tin base cathode material, nano silicon-based negative material, lithium titanate or alloy material。
The preparation of a kind of solid state lithium battery, separates both positive and negative polarity pole piece with polymerized thylene carbonate vinyl ester electrolyte, puts in metal-back, seals to obtain solid state lithium battery。
Advantage for present invention:
Do not use the lithium battery of electrode interface stabilisation of polymeric materials when first charge-discharge, can there is reduction reaction in electrolyte on negative pole, generates solid electrolyte interface, in turn results in the loss of irreversible capacity。In charge and discharge process subsequently, electrolyte can continue to react at electrode surface, makes solid electrolyte interface continued propagation。This phenomenon can make electrolyte and lithium ion continue to consume, and causes the decay of solid lithium battery cycle life。It addition, the solid electrolyte interface of growth, also can make the diffusion hindered of lithium ion, increase the polarization phenomena in charging process, reduce the discharge capacity of lithium ion battery。Stablize full solid state polymer material due to this electrode interface can electrode to be coated with effectively, it is to avoid electrode and directly contacting of electrolyte and the decomposition of electrolyte that causes。Compared with the solid lithium battery not using electrode interface stabilisation of polymeric materials, use the solid lithium battery of electrode interface stabilisation of polymeric materials can significantly improve the coulombic efficiency in first charge-discharge process。
The lithium sheet not using electrode interface stabilisation of polymeric materials has the generation of Li dendrite in charge and discharge process, will also result in the irreversible of lithium battery capacity, and meanwhile, Li dendrite also can pierce through barrier film, makes lithium battery have the threat of short circuit。And using on the lithium sheet of electrode interface stabilisation of polymeric materials, the phenomenon of Li dendrite substantially reduces, say, that electrode interface stabilisation of polymeric materials can suppress the growth of Li dendrite。Meanwhile, electrode interface is stablized full solid state polymer material and can be formed a protective layer on electrode material of lithium battery and metal lithium sheet, it is possible to effectively suppresses the destruction embedding the electrode crystal caused with deviating from of lithium ion, and then improves the cycle performance of lithium battery。
Accompanying drawing explanation
Fig. 1 is the LiFePO comprising PVCA polymer in embodiment 14Long circulating performance with the lithium battery that the lithium metal not comprising PVCA polymer assembles。
Fig. 2 is the charging and discharging curve of the negative pole half-cell that the graphite comprising PVCA polymer in embodiment 2 assembles with the lithium metal not comprising PVCA polymer。
Fig. 3 is the LiFe comprising PVCA polymer in embodiment 30.2Mn0.8PO4With comprise PVCA polymer the charging and discharging curve of full battery that assembles of graphite。
Detailed description of the invention
Embodiment 1:
Adding in VCA by AIBN under argon shield, the mass fraction of AIBN is 0.1%；40oAt C temperature, stir 24 hours, obtain PVCA polymer；PVCA polymer is dissolved in DMF, is made into the solution of 2wt.%。Lithium battery LiFePO is prepared for binding agent with PVCA polymer4Electrode plates, the mass fraction of binding agent is 10%；By LiFePO4Electrode plates is immersed in PVCA solution after 1 minute and takes out；60oUnder C, vacuum drying guarantees that solvent volatilizees completely in 24 hours, obtains the LiFePO of PVCA polymer overmold4Electrode plates。
As shown in table 1 for preparing the material assembling lithium ion battery, negative pole is uncoated lithium metal, and solid electrolyte is the PVCA/LiDFOB all solid state electrolyte that in-situ polymerization obtains, and the ion battery initial charge specific capacity prepared is 122mAhg-1, first discharge specific capacity is 119mAhg-1, coulombic efficiency is 97.5% first。
Table 1:
| Positive pole | Negative pole | Electrolyte | Initial charge specific capacity (1 C) | First discharge specific capacity (1 C) | Coulombic efficiency (%) first |
| LiFePO4 | Li | PVCA/LiDFOB | 122 | 119 | 97.5 |
Embodiment 2:
Adding in VCA by BPO under argon shield, the mass fraction of BPO is 0.5%；80oAt C temperature, stir 2 hours, obtain PVCA polymer；PVCA polymer is dissolved in DMF, is made into the solution of 5wt.%。Preparing lithium battery graphite electrode pole piece with PVCA polymer for binding agent, the mass fraction of binding agent is 5%；Graphite electrode pole piece is immersed in PVCA solution after 5 minutes and takes out；60oUnder C, vacuum drying guarantees that solvent volatilizees completely in 24 hours, obtains the graphite electrode pole piece of PVCA polymer overmold。
As shown in table 1 for preparing the material assembling lithium ion battery, reference electrode is uncoated lithium metal, and solid electrolyte is the PVCA/LiTFSI all solid state electrolyte that in-situ polymerization obtains, and the ion battery initial charge specific capacity prepared is 336mAhg-1, first discharge specific capacity is 289mAhg-1, coulombic efficiency is 86.1% first。
Table 2:
| Negative pole | Reference negative pole | Electrolyte | Initial charge specific capacity (0.2 C) | First discharge specific capacity (0.2 C) | Coulombic efficiency (%) first |
| Graphite | Li | PVCA/LiTFSI | 336 | 289 | 86.1 |
Embodiment 3:
Adding in VCA by AIBN under argon shield, the mass fraction of AIBN is 1%；60oAt C temperature, stir 12 hours, obtain PVCA polymer；PVCA polymer is dissolved in DMF, is made into the solution of 20wt.%。Lithium battery LiFe is prepared for binding agent with PVCA polymer0.2Mn0.8PO4Electrode plates, the mass fraction of binding agent is 20%；By LiFe0.2Mn0.8PO4Electrode plates is immersed in PVCA solution after 1 minute and takes out；60oUnder C, vacuum drying guarantees that solvent volatilizees completely in 24 hours, obtains the LiFe of PVCA polymer overmold0.2Mn0.8PO4Electrode plates。Preparing lithium battery graphite electrode pole piece with PVCA polymer for binding agent, the mass fraction of binding agent is 5%；Graphite electrode pole piece is immersed in PVCA solution after 2 minutes and takes out；60oUnder C, vacuum drying guarantees that solvent volatilizees completely in 24 hours, obtains the graphite electrode pole piece of PVCA polymer overmold。
As shown in table 1 for preparing the material assembling lithium ion battery, solid electrolyte is the PVCA/LiBOB all solid state electrolyte that in-situ polymerization obtains, and the ion battery initial charge specific capacity prepared is 132mAhg-1, first discharge specific capacity is 120mAhg-1, coulombic efficiency is 90.9% first。
Table 3:
| Positive pole | Negative pole | Electrolyte | Initial charge specific capacity (1 C) | First discharge specific capacity (1 C) | Coulombic efficiency (%) first |
| LiFe0.2Mn0.8PO4 | Graphite | PVCA/LiBOB | 132 | 120 | 90.9 |
Embodiment 4:
Being added by ABVN under argon shield in the mixed solution (m:m=1:1) of VCA and MAH, the mass fraction of ABVN is 1%；60oAt C temperature, stir 5 hours, obtain PVCA-MAH copolymer；PVCA-MAH copolymer is dissolved in DMF, is made into the solution of 50wt.%。Lithium battery LiCoO is prepared for binding agent with PVCA-MAH copolymer2Electrode plates, the mass fraction of binding agent is 30%；By LiCoO2Electrode plates is immersed in PVCA-MAH solution after 1 minute and takes out；60oUnder C, vacuum drying guarantees that solvent volatilizees completely in 24 hours, obtains the LiCoO of PVCA-MAH copolymer cladding2Electrode plates。The graphite electrode pole piece preparing lithium battery for binding agent with PVCA-MAH copolymer is immersed in PVCA-MAH solution after 10 minutes and takes out；60oUnder C, vacuum drying guarantees that solvent volatilizees completely in 48 hours, obtains the graphite electrode pole piece of PVCA-MAH copolymer cladding。
As shown in table 4 for preparing the material assembling lithium ion battery, solid electrolyte is the PVCA-MAH/LiDFOB all solid state electrolyte that in-situ polymerization obtains, and the ion battery initial charge specific capacity prepared is 136mAhg-1, first discharge specific capacity is 122mAhg-1, coulombic efficiency is 89.7% first。
Table 4:
| Positive pole | Negative pole | Electrolyte | Initial charge specific capacity (1 C) | First discharge specific capacity (1 C) | Coulombic efficiency (%) first |
| LiCoO2 | Graphite | PVCA-MAH/LiDFOB | 136 | 122 | 89.7 |
Embodiment 5:
Being added by AIBME under argon shield in the mixed solution (m:m=8:2) of VCA and AN, the mass fraction of AIBME is 0.1%；40oAt C temperature, stir 24 hours, obtain PVCA-AN copolymer；PVCA-AN copolymer is dissolved in DMF, is made into the solution of 30wt.%。Lithium battery LiNi is prepared for binding agent with PVCA-AN copolymer0.5Mn1.5O4Electrode plates, the mass fraction of binding agent is 10%；By LiNi0.5Mn1.5O4Electrode plates is immersed in PVCA-AN solution after 1 minute and takes out；60oUnder C, vacuum drying guarantees that solvent volatilizees completely in 24 hours, obtains the LiNi of PVCA-AN copolymer cladding0.5Mn1.5O4Electrode plates。Lithium metal pole piece is immersed in PVCA-AN solution after 40 minutes and takes out；At room temperature vacuum drying guarantees that solvent volatilizees completely in 48 hours, obtains the lithium electrode pole piece of PVCA-AN copolymer cladding。
As shown in table 5 for preparing the material assembling lithium ion battery, solid electrolyte is the PVCA-AN/LiTFSI all solid state electrolyte that in-situ polymerization obtains, the ion battery initial charge specific capacity prepared is 141mAhg-1, first discharge specific capacity is 133mAhg-1, coulombic efficiency is 94.3% first。
Table 5:
| Positive pole | Negative pole | Electrolyte | Initial charge specific capacity (1 C) | First discharge specific capacity (1 C) | Coulombic efficiency (%) first |
| LiNi0.5Mn1.5O4 | Li | PVCA-AN/LiTFSI | 141 | 133 | 94.3 |
Embodiment 6:
Being added by TBPB under argon shield in the mixed solution (m:m=2:8) of VCA and MMA, the mass fraction of TBPB is 0.1%；80oAt C temperature, stir 2 hours, obtain PVCA-MMA copolymer；PVCA-MMA copolymer is dissolved in DMF, is made into the solution of 40wt.%。Preparing lithium battery Ni-Co-Mn tertiary cathode material electrode plates with PVCA-MMA copolymer for binding agent, the mass fraction of binding agent is 30%；Ni-Co-Mn tertiary cathode material electrode plates is immersed in PVCA-MMA solution after 5 minutes and takes out；60oUnder C, vacuum drying guarantees that solvent volatilizees completely in 24 hours, obtains the Ni-Co-Mn tertiary cathode material electrode plates of PVCA-MMA copolymer cladding。Lithium metal pole piece is immersed in PVCA-MMA solution after 50 minutes and takes out；At room temperature vacuum drying guarantees that solvent volatilizees completely in 48 hours, obtains the lithium electrode pole piece of PVCA-MMA copolymer cladding。
As shown in table 6 for preparing the material assembling lithium ion battery, solid electrolyte is the PVCA-MMA/LiBOB all solid state electrolyte that in-situ polymerization obtains, and the ion battery initial charge specific capacity prepared is 167mAhg-1, first discharge specific capacity is 153mAhg-1, coulombic efficiency is 91.6% first。
Table 6:
| Positive pole | Negative pole | Electrolyte | Initial charge specific capacity (1 C) | First discharge specific capacity (1 C) | Coulombic efficiency (%) first |
| Ni-Co-Mn tertiary cathode material | Li | PVCA-MMA/LiBOB | 167 | 153 | 91.6 |
Embodiment 7:
Being added by AIBN under argon shield in the mixed solution (m:m=9:1) of VCA and AM, the mass fraction of AIBN is 0.1%；60oAt C temperature, stir 16 hours, obtain PVCA-AM copolymer；PVCA-AM copolymer is dissolved in DMF, is made into the solution of 10wt.%。Lithium battery LiFePO is prepared for binding agent with PVCA-AM polymer4Electrode plates, the mass fraction of binding agent is 5%；By LiFePO4Electrode plates dipping PVCA-AM solution took out after 2 minutes；60oUnder C, vacuum drying guarantees that solvent volatilizees completely in 24 hours, obtains the LiFePO of PVCA-AM copolymer cladding4Electrode plates。Lithium metal pole piece is immersed in PVCA-AM solution after 45 minutes and takes out；At room temperature vacuum drying guarantees that solvent volatilizees completely in 48 hours, obtains the lithium electrode pole piece of PVCA-AM copolymer cladding。
As shown in table 7 for preparing the material assembling lithium ion battery, solid electrolyte is the PVCA-AM/LiBF that in-situ polymerization obtains4All solid state electrolyte, the ion battery initial charge specific capacity prepared is 142mAhg-1, first discharge specific capacity is 134mAhg-1, coulombic efficiency is 94.4% first。
Table 7:
| Positive pole | Negative pole | Electrolyte | Initial charge specific capacity (1 C) | First discharge specific capacity (1 C) | Coulombic efficiency (%) first |
| LiFePO4 | Li | PVCA-AM/LiBF4 | 142 | 134 | 94.4 |
Embodiment 8:
Being added by TBPB under argon shield in the mixed solution (m:m=1:9) of VCA and ECA, the mass fraction of TBPB is 0.1%；80oAt C temperature, stir 12 hours, obtain PVCA-ECA copolymer；PVCA-ECA copolymer is dissolved in DMF, is made into the solution of 25wt.%。Lithium battery LiCoO is prepared for binding agent with PVCA-ECA polymer2Electrode plates, the mass fraction of binding agent is 10%；By LiCoO2Electrode plates is immersed in PVCA-ECA solution after 5 minutes and takes out；60oUnder C, vacuum drying guarantees that solvent volatilizees completely in 24 hours, obtains the LiCoO of PVCA-ECA copolymer cladding2Tertiary cathode material electrode plates。Lithium metal pole piece is immersed in PVCA-ECA solution after 40 minutes and takes out；At room temperature vacuum drying guarantees that solvent volatilizees completely in 48 hours, obtains the lithium electrode pole piece of PVCA-ECA copolymer cladding。
As shown in table 8 for preparing the material assembling lithium ion battery, solid electrolyte is the PVCA-ECA/LiBOB all solid state electrolyte that in-situ polymerization obtains, and the ion battery initial charge specific capacity prepared is 135mAhg-1, first discharge specific capacity is 121mAhg-1, coulombic efficiency is 89.6% first。
Table 8:
| Positive pole | Negative pole | Electrolyte | Initial charge specific capacity (1 C) | First discharge specific capacity (1 C) | Coulombic efficiency (%) first |
| LiCoO2 | Li | PVCA-ECA/LiBOB | 135 | 121 | 89.6 |
Claims (9)
1. the electrode of lithium cell preparation method comprising interface stability polymeric material, it is characterised in that interface stability polymer is polymerized thylene carbonate vinyl acetate or its copolymer, and electrode preparation method key step is as follows:
1) vinylene carbonate or the multi-component copolymer monomer containing vinylene carbonate carry out polymerisation in bulk under the initiation of initiator and obtain electrode interface stabilisation of polymeric materials；
2) being dissolved in DMF (DMF) by electrode interface stabilisation of polymeric materials, obtain polymer solution, wherein electrode of lithium cell interface stability polymeric material mass fraction in a polymer solution is 2%-50%；
3) preparing anode for lithium battery pole piece and cathode pole piece with electrode of lithium cell interface stability polymeric material for binding agent, binding agent mass fraction in electrode material is 5%-30%；
4) prepared electrode plates or metal lithium electrode immersing taking-up after 1-60 minute in above-mentioned polymer solution, vacuum drying obtains solid state lithium battery electrode。
2. a kind of electrode of lithium cell preparation method comprising interface stability polymeric material described in claim 1, it is characterised in that:
The structure of electrode of lithium cell interface stability polymeric material is as follows:
；；；；；；；；；
Wherein m is the degree of polymerization of vinylene carbonate construction unit, and span is 2-105；N is the degree of polymerization of comonomer, and span is 0-105。
3. a kind of electrode of lithium cell preparation method comprising interface stability polymeric material described in claim 1, it is characterised in that: to vinylene carbonate or containing in vinylene carbonate multi-component copolymer monomer add mass fraction be the initiator of 0.1%-1.0%；The solution adding initiator is placed in 40-80oIt is polymerized 2-24 hour under C, namely obtains polymerized thylene carbonate vinyl acetate or polymerized thylene carbonate vinyl ester copolymers；In copolymer, vinylene carbonate construction unit mass fraction in the copolymer is 10%-99%。
4. a kind of electrode of lithium cell preparation method comprising interface stability polymeric material described in claim 1, it is characterised in that: described initiator is the one in azodiisobutyronitrile (AIBN), 2,2'-Azobis(2,4-dimethylvaleronitrile) (ABVN), azo-bis-iso-dimethyl (AIBME), benzoyl peroxide (BPO), the benzoyl peroxide tert-butyl ester (TBPB), methyl ethyl ketone peroxide (MEKPO)。
5. a kind of electrode of lithium cell preparation method comprising interface stability polymeric material described in claim 1, it is characterised in that: electrode of lithium cell interface stability polymeric material thickness on anode pole piece, cathode pole piece or lithium metal is 0.05-10 μm。
6. a kind of electrode of lithium cell preparation method comprising interface stability polymeric material described in a claim 1, it is characterised in that: the active material of described positive pole includes LiFePO4 (LiFePO4), iron manganese phosphate for lithium (LiFe0.2Mn0.8PO4), cobalt acid lithium (LiCoO2), LiMn2O4 (LiMn2O4), nickel ion doped (LiNi0.5Mn1.5O4), nickel cobalt aluminum or nickel-cobalt-manganese ternary material electrodes；
The active material of described negative pole includes lithium metal, graphite, amorphous carbon, carbonaceous mesophase spherules, silicon-carbon cathode, tin base cathode material, nano silicon-based negative material, lithium titanate or alloy material。
7. the electrode of lithium cell comprising interface stability polymeric material that prepared by the preparation method described in claim 1 application in solid state lithium battery。
8. a solid state lithium battery, including positive pole, negative pole, electrolyte between both positive and negative polarity, it is characterized in that: positive pole and negative pole are the lithium battery anode comprising interface stability polymeric material prepared of preparation method according to claim 1 and negative pole, electrolyte between both positive and negative polarity is polymerized thylene carbonate vinyl ester electrolyte
The active material of described positive pole includes LiFePO4 (LiFePO4), iron manganese phosphate for lithium (LiFe0.2Mn0.8PO4), cobalt acid lithium (LiCoO2), LiMn2O4 (LiMn2O4), nickel ion doped (LiNi0.5Mn1.5O4), nickel cobalt aluminum or nickel-cobalt-manganese ternary material electrodes；
The active material of described negative pole includes lithium metal, graphite, amorphous carbon, carbonaceous mesophase spherules, silicon-carbon cathode, tin base cathode material, nano silicon-based negative material, lithium titanate or alloy material。
9. the preparation of a solid state lithium battery, it is characterised in that: with polymerized thylene carbonate vinyl ester electrolyte, both positive and negative polarity pole piece is separated, put in metal-back, seal to obtain solid state lithium battery。
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