CN103000939B - Lithium ion battery with graphene composite membrane as current collector and preparation method thereof - Google Patents
Lithium ion battery with graphene composite membrane as current collector and preparation method thereof Download PDFInfo
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- CN103000939B CN103000939B CN201210532017.2A CN201210532017A CN103000939B CN 103000939 B CN103000939 B CN 103000939B CN 201210532017 A CN201210532017 A CN 201210532017A CN 103000939 B CN103000939 B CN 103000939B
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- lithium
- current collector
- graphene composite
- ion battery
- lithium ion
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 43
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 37
- 239000002131 composite material Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000012528 membrane Substances 0.000 title abstract 4
- 239000003792 electrolyte Substances 0.000 claims abstract description 20
- 239000000463 material Substances 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 8
- 239000000843 powder Substances 0.000 claims abstract description 7
- 239000002002 slurry Substances 0.000 claims abstract description 7
- 239000007773 negative electrode material Substances 0.000 claims abstract description 5
- 239000007774 positive electrode material Substances 0.000 claims abstract description 5
- 229920006280 packaging film Polymers 0.000 claims abstract description 4
- 239000012785 packaging film Substances 0.000 claims abstract description 4
- 239000000654 additive Substances 0.000 claims description 14
- 230000000996 additive effect Effects 0.000 claims description 14
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 13
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 10
- 229910052744 lithium Inorganic materials 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 9
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 8
- 239000004917 carbon fiber Substances 0.000 claims description 8
- 239000002041 carbon nanotube Substances 0.000 claims description 7
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 6
- 229910002804 graphite Inorganic materials 0.000 claims description 6
- 239000010439 graphite Substances 0.000 claims description 6
- 229910003002 lithium salt Inorganic materials 0.000 claims description 6
- 159000000002 lithium salts Chemical class 0.000 claims description 6
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 claims description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 5
- 229920006267 polyester film Polymers 0.000 claims description 5
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000011230 binding agent Substances 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 4
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 claims description 4
- 239000011812 mixed powder Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 229910010707 LiFePO 4 Inorganic materials 0.000 claims description 3
- 230000004888 barrier function Effects 0.000 claims description 3
- ANLVEXKNRYNLDH-UHFFFAOYSA-N 1,3-dioxonan-2-one Chemical compound O=C1OCCCCCCO1 ANLVEXKNRYNLDH-UHFFFAOYSA-N 0.000 claims description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims description 2
- UHOPWFKONJYLCF-UHFFFAOYSA-N 2-(2-sulfanylethyl)isoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(CCS)C(=O)C2=C1 UHOPWFKONJYLCF-UHFFFAOYSA-N 0.000 claims description 2
- 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 claims description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 2
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- ZVKRVGZVXQYLPZ-UHFFFAOYSA-N [Li].[V].P(O)(O)(O)=O Chemical compound [Li].[V].P(O)(O)(O)=O ZVKRVGZVXQYLPZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 239000003963 antioxidant agent Substances 0.000 claims description 2
- 230000003078 antioxidant effect Effects 0.000 claims description 2
- 229940043232 butyl acetate Drugs 0.000 claims description 2
- 229930188620 butyrolactone Natural products 0.000 claims description 2
- SIXOAUAWLZKQKX-UHFFFAOYSA-N carbonic acid;prop-1-ene Chemical compound CC=C.OC(O)=O SIXOAUAWLZKQKX-UHFFFAOYSA-N 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 229940093499 ethyl acetate Drugs 0.000 claims description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 2
- 239000003063 flame retardant Substances 0.000 claims description 2
- 229910021385 hard carbon Inorganic materials 0.000 claims description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 2
- ALTVCFKRYOLNPF-UHFFFAOYSA-N imino(trifluoromethyl)sulfanium Chemical compound FC(F)(F)[S+]=N ALTVCFKRYOLNPF-UHFFFAOYSA-N 0.000 claims description 2
- OVAQODDUFGFVPR-UHFFFAOYSA-N lithium cobalt(2+) dioxido(dioxo)manganese Chemical compound [Li+].[Mn](=O)(=O)([O-])[O-].[Co+2] OVAQODDUFGFVPR-UHFFFAOYSA-N 0.000 claims description 2
- DEUISMFZZMAAOJ-UHFFFAOYSA-N lithium dihydrogen borate oxalic acid Chemical compound B([O-])(O)O.C(C(=O)O)(=O)O.C(C(=O)O)(=O)O.[Li+] DEUISMFZZMAAOJ-UHFFFAOYSA-N 0.000 claims description 2
- -1 lithium fluoroborate Chemical compound 0.000 claims description 2
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 2
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 2
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 2
- ILXAVRFGLBYNEJ-UHFFFAOYSA-K lithium;manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[O-]P([O-])([O-])=O ILXAVRFGLBYNEJ-UHFFFAOYSA-K 0.000 claims description 2
- 229940017219 methyl propionate Drugs 0.000 claims description 2
- KKQAVHGECIBFRQ-UHFFFAOYSA-N methyl propyl carbonate Chemical compound CCCOC(=O)OC KKQAVHGECIBFRQ-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 229940090181 propyl acetate Drugs 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 229910021384 soft carbon Inorganic materials 0.000 claims description 2
- 239000003381 stabilizer Substances 0.000 claims description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000010949 copper Substances 0.000 abstract description 14
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 7
- 229910052802 copper Inorganic materials 0.000 abstract description 6
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- 238000004090 dissolution Methods 0.000 abstract description 2
- 238000001035 drying Methods 0.000 abstract 1
- 238000005096 rolling process Methods 0.000 abstract 1
- 238000007581 slurry coating method Methods 0.000 abstract 1
- 239000000758 substrate Substances 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 8
- 229910013870 LiPF 6 Inorganic materials 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- 239000004411 aluminium Substances 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 238000012856 packing Methods 0.000 description 4
- 229910013528 LiN(SO2 CF3)2 Inorganic materials 0.000 description 3
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 229910013872 LiPF Inorganic materials 0.000 description 2
- 101150058243 Lipf gene Proteins 0.000 description 2
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000002134 carbon nanofiber Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 230000004087 circulation Effects 0.000 description 1
- ZGDWHDKHJKZZIQ-UHFFFAOYSA-N cobalt nickel Chemical compound [Co].[Ni].[Ni].[Ni] ZGDWHDKHJKZZIQ-UHFFFAOYSA-N 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to a lithium ion battery with a graphene composite membrane as a current collector and a preparation method thereof. The lithium ion battery comprises a positive electrode, a negative electrode, a separator and an electrolyte, which are sealed in a packaging film. The positive electrode comprises a positive current collector and a positive active material coated on the current collector; the negative electrode comprises a negative current collector and a negative active material coated on the current collector; the positive current collector and the negative current collector are both graphene composite membrane; the graphene composite membrane is divided into three layers; a middle layer is a substrate; and both sides of the middle layer are conductive films mainly consisting of a graphene powder material. The preparation method comprises conductive film slurry preparation, conductive film slurry coating, drying and rolling. Compared with the prior art, the battery provided by the method can obtain better high temperature properties and safety performance, fundamentally eliminate electrochemical dissolution of a metal copper current collector caused by overdischarge of the battery, and improve safety of battery in the case of abuse usage.
Description
Technical field
The invention belongs to field of lithium ion battery, more particularly, the present invention relates to a kind of take graphene composite film as lithium ion battery of collector body and preparation method thereof.
Background technology
Traditional lithium ion battery selects metallic aluminium (Al) paper tinsel and metallic copper (Cu) paper tinsel respectively as positive electrode collector and negative electrode collector usually, LiPF
6carbonate solution as electrolyte.Wherein LiPF
6thermal stability poor, its decomposition temperature is in organic solvent about 80 DEG C, which greatly limits with LiPF
6for the application in high temperature environments of electrolytical conventional lithium ion battery.Lithium ion battery traditional in addition, when battery temperature raises, what electrolyte almost take part in that inside battery occurs responding, and not only comprises reacting to each other between electrolyte and negative material, positive electrode, comprises the decomposition reaction of electrolyte self simultaneously.The decomposition reaction temperature of electrolyte is generally greater than 200 DEG C, heat about the 250J/g of generation.Be seen in a lot of reports about lithium-ion safe problem of space in a newspaper, all have contacting more or less with the unsteadiness of electrolyte and electrolyte.LiCF
3sO
3, LiN (SO
2cF
3)
2, the relative LiPF of lithium salts such as LiTFSI
6there is higher heat decomposition temperature, the lithium ion battery electrolyte applied under being more suitable for doing hot environment, it is as electrolysis additive in addition, more stable SEI film can be formed between graphite cathode and electrolyte, effectively can improve the stability that lithium ion battery circulates under high temperature (more than 60 DEG C) environment, but LiCF
3sO
3, LiN (SO
2cF
3)
2, the lithium salts such as LiTFSI all has corrosiveness to positive pole aluminium (Al) collector body that conventional lithium ion battery uses, and thus limits its application in conventional lithium ion battery.
In addition, metallic copper (Cu) collector body that conventional lithium ion battery uses easily causes the dissolving of Cu when battery over-discharge, charge after putting, the Cu ion of dissolving can move to positive pole and separate out Cu metal again, very easily causes internal short-circuit and then causes safety problem.
Graphene replaces the metal current collector of lithium ion battery as excellent conductive heat conducting material, greatly can widen the range of choice of lithium ion battery electrolyte, and then improve thermally-stabilised row and the fail safe of lithium ion battery, widen the range of application of lithium ion battery, Columbia Univ USA researcher points out: when the number of plies of graphite flake is more than or equal to 9, performance is the character of graphite, and will show the new kink characteristics of Graphene when the number of plies of graphite flake is less than 9! The Chinese invention patent being CN101572327A as publication number discloses one " Graphene is the lithium ion battery of negative material " on November 4th, 2009, and Graphene is compressed in copper foil current collector by low temperature manufacturing process by it, but positive pole is still traditional material.Publication number is that the Chinese invention patent of CN102412396A disclosed " a kind of lithium ion battery electrode material of discontinuous graphene coated " on April 11st, 2012, and its negative or positive electrode selects an employing sintering process by discontinuous for the Graphene surface being coated on electrode base material.
There is no a kind of positive pole at present and negative pole all adopts Heat stability is good, anti-puncture ability is strong, the lithium ion battery of the graphene composite film that electrolyte easily infiltrates.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, provide a kind of positive pole and negative pole all to adopt Heat stability is good, anti-puncture ability is strong, the lithium ion battery of the graphene composite film that electrolyte easily infiltrates.
Another object of the present invention is to provide the method preparing this graphene composite film collector body.
To achieve these goals, the present invention adopts following technical scheme:
This take graphene composite film as the lithium ion battery of collector body, it comprises the positive pole be sealed in packaging film, negative pole, barrier film and electrolyte, described positive pole comprises positive electrode collector and coating positive active material on the current collector, described negative pole comprises negative electrode collector and coating negative electrode active material on the current collector, it is characterized in that described positive electrode collector and negative electrode collector are graphene composite film, described graphene composite film is divided into three layers, intermediate layer is base material, and the both sides in intermediate layer are the conducting film mainly comprising Graphene powder composition.
Preferably, described base material is polyester film; For reducing its cost, also add in carbon fiber, carbon nano-tube, conductive carbon black in described conducting film composition one or more.
Further, described positive active material is selected from cobalt acid lithium, lithium nickelate, LiMn2O4, nickle cobalt lithium manganate, LiFePO 4, lithium manganese phosphate, one or more in phosphoric acid vanadium lithium; Described negative electrode active material be selected from Delanium, native graphite, mesophase carbon fiber ball, mesophase carbon fiber, soft carbon, hard carbon, lithium titanate, silicon and unformed silica one or more; Described electrolyte comprises lithium salts, nonaqueous solvents and additive, and wherein, lithium salts is selected from lithium hexafluoro phosphate (LiPF
6), one or more in the two lithium fluoroborate of LiBF4, bis trifluoromethyl sulfimide base lithium (LiTFSI), di-oxalate lithium borate, oxalic acid, lithium perchlorate; Nonaqueous solvents be selected from ethylene carbonate (EC), propene carbonate, butylene, dimethyl carbonate (DMC), diethyl carbonate, methyl ethyl carbonate (EMC), methyl propyl carbonate, butyrolactone, ethyl acetate, propyl acetate, butyl acetate, methyl propionate, ethyl propionate, propyl propionate one or more; Additive be selected from SEI film for additive, anti-overcharge additive, flame-retardant additive, electrolyte stabilizing agent, raising conductivity additive, antioxidant one or more.
Take graphene composite film as the preparation method of the lithium ion battery of collector body, it, particularly in the preparation method of graphene composite film, comprises following steps:
A) mixed powder and binding agent powder that comprise Graphene are added in solvent by dry weight than 70: 30-95: 5, after Homogeneous phase mixing, make conducting film slurry for subsequent use;
B) then by step a) in obtained conducting film slurry, be evenly coated on base material that thickness is 5um-20um, adopt the double spread method of upper and lower surface, two sided coatings weight is consistent;
C) finally oven dry, roll-in, after roll-in, THICKNESS CONTROL is at 8um-30um.
As preferably, step a) described in powder also comprise in carbon fiber (VGCF), carbon nano-tube (CNT), conductive carbon black (SP) one or more; Described solvent comprises 1-METHYLPYRROLIDONE (NMP); Step b) described in base material comprise polyester film.
The present invention compared with prior art, owing to employing the collector body of graphene composite film as positive pole, thus avoids LiTFSI, LiCF
3sO
3, LiN (SO
2cF
3)
2deng as electrolyte or electrolysis additive to the corrosion of positive electrode collector, thus obtain better hot properties and security performance.In addition, lithium ion battery of the present invention have employed graphene composite film as negative electrode collector, fundamentally stop metallic copper (Cu) collector body to cross because of battery and put and the problem of the electrochemical dissolution occurred, improve battery fail safe in abuse conditions.
Embodiment
Embodiment 1
Be be dissolved in the mixed powder of Graphene and carbon nano-tube (CNT) and Kynoar (PVDF) in 1-METHYLPYRROLIDONE (NMP) solvent make conducting film slurry at 95: 5 by dry weight ratio, then obtained conducting film slurry is coated on the upper and lower surface of polyester film, graphene composite film is made in finally oven dry, roll-in, and graphene composite film makes collector body through cross cutting.
With known technology by LiMn2O4, conductive agent, binding agent mixed pulp, coat on graphene composite film collector body, dry, cut after compressing tablet and obtain positive plate; By Delanium, conductive agent, adhesive mixed pulp, coat on Graphene collector body, dry, cut after compressing tablet and obtain negative plate; With barrier film positive plate and negative plate separated and reel and make battery; This battery is placed in plastic-aluminum packaging film, wraps up; First battery is packaged into pouch-type, then by the electrolyte solution inlet sack-type packaging of the LiTFSI/EC+DMC+EMC of 1mol/L; After changing into process, battery is carried out last heat-sealing together, make flexible packing lithium ion battery.
Embodiment 2
Basic with embodiment 1, unlike: take mol ratio as LiPF
6: LiTFSI=70: 30 replace LiTFSI
Embodiment 3
Basic with embodiment 1, unlike: replace LiMn2O4 with LiFePO 4;
Embodiment 4
Basic with embodiment 2, unlike: replace LiMn2O4 with cobalt nickel ion doped;
Comparative example 1
Only change the positive electrode collector graphene composite film in embodiment 1 into traditional aluminium (Al) paper tinsel, negative electrode collector graphene composite film changes traditional copper (Cu) paper tinsel into.Flexible packing lithium ion battery is made again by above-mentioned same procedure.
Comparative example 2
Only change the positive electrode collector graphene composite film in embodiment 2 into traditional aluminium (Al) paper tinsel, negative electrode collector graphene composite film changes traditional copper (Cu) paper tinsel into.Flexible packing lithium ion battery is made again by above-mentioned same procedure.
Comparative example 3
Only the LiTFSI/EC+DMC+EMC solution of the 1mol/L in comparative example 1 is changed into the LiPF of 1mol/L
6/ EC+DMC+EMC solution.
The flexible packing lithium ion battery that Example 1-4 and comparative example 1-4 obtains does contrast test.Content measurement comprises uses the 1C charge and discharge cycles capability retention of 500 weeks at different temperatures, the internal resistance rate of change of 45 DEG C of circulations after 500 weeks; Cell thickness after storing 8 hours under the lower 85 DEG C of environment of full power state, the rate of change of internal resistance and capacity.
Table 1
Find out from comparing result, lithium ion battery of the present invention relatively and conventional lithium ion battery there is better high temperature cyclic performance.
Table two
| Group | Thickness change | Internal resistance rate of change | Residual capacity | Reversible capacity |
| Embodiment 1 (4.3V) | 4％ | 15％ | 80％ | 92％ |
| Embodiment 2 (4.3V) | 5％ | 18％ | 77％ | 90％ |
| Embodiment 3 (3.6V) | 3％ | 11％ | 85％ | 94％ |
| Embodiment 4 (3.6V) | 4％ | 23％ | 81％ | 91％ |
| Comparative example 1 (4.3V) | 10％ | 25％ | 70％ | 80％ |
| Comparative example 2 (4.3V) | 15％ | 30％ | 66％ | 77％ |
| Comparative example 3 (4.3V) | 70％ | 58％ | 60％ | 73％ |
Find out from comparing result, lithium ion battery of the present invention relatively and conventional lithium ion battery there is better high-temperature storage characteristics.
According to above-mentioned principle, the present invention can also carry out suitable change and amendment to above-mentioned embodiment.Therefore, the present invention is not limited to embodiment disclosed and described above, also should fall in the protection range of claim of the present invention modifications and changes more of the present invention.In addition, although employ some specific terms in this specification, these terms just for convenience of description, do not form any restriction to the present invention.
Claims (3)
1. be the lithium ion battery of collector body with graphene composite film, it comprises the positive pole be sealed in packaging film, negative pole, barrier film and electrolyte, described positive pole comprises positive electrode collector and coating positive active material on the current collector, described negative pole comprises negative electrode collector and coating negative electrode active material on the current collector, it is characterized in that described positive electrode collector and negative electrode collector are graphene composite film, described graphene composite film is divided into three layers, intermediate layer is base material, and the both sides in intermediate layer are the conducting film mainly comprising Graphene powder composition;
Described base material is polyester film, also comprises one or more in carbon fiber, carbon nano-tube, conductive carbon black in described conducting film composition.
2. according to claim 1 take graphene composite film as the lithium ion battery of collector body, it is characterized in that described positive active material is selected from cobalt acid lithium, lithium nickelate, LiMn2O4, nickle cobalt lithium manganate, LiFePO 4, lithium manganese phosphate, phosphoric acid vanadium lithium one or more; Described negative electrode active material be selected from Delanium, native graphite, mesophase carbon fiber ball, mesophase carbon fiber, soft carbon, hard carbon, lithium titanate, silicon and unformed silica one or more; Described electrolyte comprises lithium salts, nonaqueous solvents and additive, wherein, lithium salts be selected from lithium hexafluoro phosphate, LiBF4, bis trifluoromethyl sulfimide base lithium, di-oxalate lithium borate, the two lithium fluoroborate of oxalic acid, lithium perchlorate one or more; Nonaqueous solvents be selected from ethylene carbonate, propene carbonate, butylene, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, methyl propyl carbonate, butyrolactone, ethyl acetate, propyl acetate, butyl acetate, methyl propionate, ethyl propionate, propyl propionate one or more; Additive be selected from SEI film for additive, anti-overcharge additive, flame-retardant additive, electrolyte stabilizing agent, raising conductivity additive, antioxidant one or more.
3. be the preparation method of the lithium ion battery of collector body with graphene composite film, it is characterized in that the preparation method of graphene composite film, comprise following steps:
A) mixed powder and binding agent powder that comprise Graphene are added in solvent by dry weight than 70: 30-95: 5, after Homogeneous phase mixing, make conducting film slurry for subsequent use;
B) then by step a) in obtained conducting film slurry, be evenly coated on base material that thickness is 5um-20um, adopt the double spread method of upper and lower surface, two sided coatings weight is consistent;
C) finally oven dry, roll-in, after roll-in, THICKNESS CONTROL is at 8um-30um;
Step a) described in the mixed powder comprising Graphene also comprise in carbon fiber, carbon nano-tube, conductive carbon black one or more; Described binding agent powder is Kynoar; Described solvent comprises 1-METHYLPYRROLIDONE; Step b) described in base material be polyester film.
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| CN103326029A (en) * | 2013-06-07 | 2013-09-25 | 深圳市海太阳实业有限公司 | Negative electrode sheet, positive electrode sheet, and lithium ion battery |
| CN104347881A (en) * | 2013-07-23 | 2015-02-11 | 中国科学院金属研究所 | Preparation method and applications of battery graphene-base current collector |
| CN104518200B (en) * | 2013-09-30 | 2017-05-17 | 万向一二三股份公司 | Graphene electric conduction glue layer-containing lithium ion battery positive electrode sheet production method |
| CN104916809B (en) * | 2014-03-12 | 2017-06-09 | 中国科学院金属研究所 | A kind of integrated flexible electrode |
| CN103950239B (en) * | 2014-04-24 | 2017-01-18 | 合肥国轩高科动力能源有限公司 | Multifunctional composite film for chemical power supply |
| CN105810950A (en) * | 2014-12-30 | 2016-07-27 | 苏州宝时得电动工具有限公司 | Battery |
| CN104377361B (en) * | 2014-10-20 | 2017-04-19 | 惠州亿纬锂能股份有限公司 | Thin diaphragm battery and preparing method thereof |
| CN105462565B (en) * | 2015-12-14 | 2018-09-21 | 德阳烯碳科技有限公司 | A kind of preparation method of graphene and carbon fiber composite heat interfacial material |
| CN105826571A (en) * | 2016-05-26 | 2016-08-03 | 江苏深苏电子科技有限公司 | Method for preparing flexible high-conductivity graphene and carbon nano tube composite current collector |
| CN106207132B (en) * | 2016-08-31 | 2019-06-14 | 深圳博磊达新能源科技有限公司 | A kind of preparation method of lithium titanate/carbon fiber/carbon nanotube/graphene quaternary composite material |
| CN110718676A (en) * | 2018-07-12 | 2020-01-21 | 中国科学技术大学 | Lithium ion battery positive pole piece, preparation method thereof and lithium ion battery |
| CN110085869B (en) * | 2019-04-30 | 2021-03-30 | 柔电（武汉）科技有限公司 | Conductive current collector, preparation method thereof, battery pole piece and lithium battery |
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