CN106935911B - Reduce the method that nickelic battery high-temperature storage produces gas - Google Patents
Reduce the method that nickelic battery high-temperature storage produces gas Download PDFInfo
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- CN106935911B CN106935911B CN201710132072.5A CN201710132072A CN106935911B CN 106935911 B CN106935911 B CN 106935911B CN 201710132072 A CN201710132072 A CN 201710132072A CN 106935911 B CN106935911 B CN 106935911B
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- 238000000034 method Methods 0.000 title claims abstract description 38
- 238000003860 storage Methods 0.000 title claims abstract description 28
- 239000003792 electrolyte Substances 0.000 claims abstract description 32
- 239000000654 additive Substances 0.000 claims abstract description 29
- 230000000996 additive effect Effects 0.000 claims abstract description 29
- 239000000463 material Substances 0.000 claims abstract description 19
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 16
- 239000000126 substance Substances 0.000 claims abstract description 15
- 238000002347 injection Methods 0.000 claims abstract description 14
- 239000007924 injection Substances 0.000 claims abstract description 14
- 238000004513 sizing Methods 0.000 claims abstract description 13
- 239000000203 mixture Substances 0.000 claims abstract description 12
- 230000005764 inhibitory process Effects 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 9
- 238000012545 processing Methods 0.000 claims abstract description 6
- SJHAYVFVKRXMKG-UHFFFAOYSA-N 4-methyl-1,3,2-dioxathiolane 2-oxide Chemical compound CC1COS(=O)O1 SJHAYVFVKRXMKG-UHFFFAOYSA-N 0.000 claims description 11
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 3
- 239000010405 anode material Substances 0.000 claims 1
- 229910052744 lithium Inorganic materials 0.000 abstract description 19
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 18
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 16
- 229910052759 nickel Inorganic materials 0.000 abstract description 10
- 238000004458 analytical method Methods 0.000 abstract description 6
- 230000002401 inhibitory effect Effects 0.000 abstract description 6
- 230000000116 mitigating effect Effects 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 41
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 10
- 239000007788 liquid Substances 0.000 description 10
- 239000011248 coating agent Substances 0.000 description 9
- 238000000576 coating method Methods 0.000 description 9
- 238000009835 boiling Methods 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 4
- 239000012752 auxiliary agent Substances 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 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 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- -1 polypropylene Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- LOURZMYQPMDBSR-UHFFFAOYSA-N 1,3,2-dioxathiane 2-oxide Chemical compound O=S1OCCCO1 LOURZMYQPMDBSR-UHFFFAOYSA-N 0.000 description 1
- MCMMCRYPQBNCPH-UHFFFAOYSA-N 13-[[2-amino-3-(4-hydroxyphenyl)propanoyl]amino]-7-benzyl-3,3,14,14-tetramethyl-6,9,12-trioxo-1,2-dithia-5,8,11-triazacyclotetradecane-4-carboxylic acid Chemical compound O=C1NCC(=O)NC(CC=2C=CC=CC=2)C(=O)NC(C(O)=O)C(C)(C)SSC(C)(C)C1NC(=O)C(N)CC1=CC=C(O)C=C1 MCMMCRYPQBNCPH-UHFFFAOYSA-N 0.000 description 1
- 239000004604 Blowing Agent Substances 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 239000005955 Ferric phosphate Substances 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 229910006025 NiCoMn Inorganic materials 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- FCVHBUFELUXTLR-UHFFFAOYSA-N [Li].[AlH3] Chemical class [Li].[AlH3] FCVHBUFELUXTLR-UHFFFAOYSA-N 0.000 description 1
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- BTGRAWJCKBQKAO-UHFFFAOYSA-N adiponitrile Chemical compound N#CCCCCC#N BTGRAWJCKBQKAO-UHFFFAOYSA-N 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- SIXOAUAWLZKQKX-UHFFFAOYSA-N carbonic acid;prop-1-ene Chemical compound CC=C.OC(O)=O SIXOAUAWLZKQKX-UHFFFAOYSA-N 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 229940032958 ferric phosphate Drugs 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 1
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 150000002696 manganese Chemical class 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- OJURWUUOVGOHJZ-UHFFFAOYSA-N methyl 2-[(2-acetyloxyphenyl)methyl-[2-[(2-acetyloxyphenyl)methyl-(2-methoxy-2-oxoethyl)amino]ethyl]amino]acetate Chemical compound C=1C=CC=C(OC(C)=O)C=1CN(CC(=O)OC)CCN(CC(=O)OC)CC1=CC=CC=C1OC(C)=O OJURWUUOVGOHJZ-UHFFFAOYSA-N 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- CWKLZLBVOJRSOM-UHFFFAOYSA-N methyl pyruvate Chemical compound COC(=O)C(C)=O CWKLZLBVOJRSOM-UHFFFAOYSA-N 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 210000003739 neck Anatomy 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000011218 segmentation Effects 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 239000011206 ternary composite Substances 0.000 description 1
- 238000009941 weaving 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or 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
- 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- 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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/44—Methods for charging or discharging
- H01M10/446—Initial charging measures
-
- 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
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- 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
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The method proposed by the present invention for reducing nickelic battery high-temperature storage and producing gas, comprising the following steps: positive electrode and inhibition are produced into gas additive and are mixed, anode sizing agent is obtained；The anode sizing agent is coated on plus plate current-collecting body, and carries out drying and processing and forms anode pole piece；By the anode pole piece and matched cathode pole piece, diaphragm assembly in battery case, injection electrolyte for the first time then is carried out to battery case；After standing specified time under assigned temperature, chemical conversion treatment is carried out；After the intracorporal gas discharge of the battery case, second of injection electrolyte is carried out.The problem of producing gas when improving the battery high-temperature storage of just extremely high-nickel material；The inhibition being added produces gas additive and only forms a film in anode, and reduction is lost on cathode, improves the utilization rate of additive；The case where being only added in anode sizing agent mix stages and inhibit to produce gas additive, both reduce the usage amount for inhibiting to produce gas additive, also mitigating anode analysis lithium.
Description
Technical field
The present invention relates to technical field of lithium batteries, especially relate to a kind of reduce nickelic battery high-temperature storage and produce gas
Method.
Background technique
Existing electric car has the advantages that environmentally protective while short there is also course continuation mileage disadvantage.In order to improve
The course continuation mileage of electric vehicle, major lithium-ion-power cell company is all in the lithium battery of Devoting Major Efforts To Developing high-energy density.Improve energy
The common method of metric density is improved positive and negative anodes gram volume, raising cell voltage, raising coating weight etc..
As the energy density of lithium battery is higher and higher, the gram volume of positive electrode is required also higher and higher.Increase just
The Ni content of pole material and the voltage of battery is improved to promote gram volume be one such measure.But it brings therewith more
Carry out more serious high temperature storage and produces gas problem.The conventional gas that overcomes the problems, such as to produce is by adding the addition for inhibiting to produce gas in electrolyte
Agent such as PS (propylene sulfite), PST (1,3- acrylic-sultones), VEC (sour vinylethylene), SN (adiponitrile) etc..
Although these schemes all play the problem of inhibition produces gas, new defect is brought --- analysis lithium, circulation deterioration are serious, influence
The working performance of battery.
Summary of the invention
The main object of the present invention is to provide a kind of method for reducing nickelic battery high-temperature storage and producing gas, is solved just extremely high
The problem of battery high-temperature storage of nickel material produces gas.
The present invention proposes a kind of method for reducing nickelic battery high-temperature storage and producing gas, comprising the following steps:
By positive electrode and inhibit to produce the mixing of gas additive, obtains anode sizing agent；
The anode sizing agent is coated on plus plate current-collecting body, and carries out drying and processing and forms anode pole piece；
By the anode pole piece and matched cathode pole piece, diaphragm assembly in battery case, then to battery case into
Row injects electrolyte for the first time；
After standing specified time under assigned temperature, chemical conversion treatment is carried out；
After the intracorporal gas discharge of the battery case, second of injection electrolyte is carried out.
Preferably, the positive electrode includes one of NCM333, NCM523, NCM622, NCM811, NCA or appoints
It anticipates several mixtures.
Preferably, described to inhibit to produce gas additive to include one of PS, PST, VEC or any several mixture.
Preferably, the additive amount for inhibiting production gas additive is the 0.1%~3% of positive quality of materials.
Preferably, in the step of first time injection electrolyte, the amount of first time electrolyte injection is positive electrode
The 0.3~0.4 of quality.
Preferably, the time for standing step is 0.5~5h.
Preferably, the progress drying and processing is formed in anode pole piece step, and drying temperature is 100~120 DEG C.
Preferably, the assigned temperature is between 55~70 DEG C.
Preferably, in the step of second of injection electrolyte, the amount that electrolyte is added is the quality of positive electrode
0.15~0.2.
The method proposed by the present invention for reducing nickelic battery high-temperature storage and producing gas, by the generation work for improving anode
Skill, when improving high-nickel material high temperature storage the problem of production gas；The inhibition being added produces gas additive and only forms a film in anode, reduces
It is lost on cathode, improves the utilization rate of additive；It is only added in anode sizing agent mix stages and inhibits to produce gas additive, both reduced
The usage amount for inhibiting production gas additive also mitigates the case where anode analyses lithium；Gram for improving lithium battery anode is also achieved simultaneously
The target of capacity.
Detailed description of the invention
Fig. 1 is the flow diagram that the present invention reduces that nickelic battery high-temperature storage produces one embodiment of method of gas；
Fig. 2 is the process flow diagram that the present invention reduces that nickelic battery high-temperature storage produces one embodiment of method of gas.
The embodiments will be further described with reference to the accompanying drawings for the realization, the function and the advantages of the object of the present invention.
Specific embodiment
It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, it is not intended to limit the present invention.
Referring to Fig.1, the present invention proposes a kind of method for reducing nickelic battery high-temperature storage and producing gas, comprising the following steps:
S1, positive electrode and inhibition are produced into the mixing of gas additive, obtains anode sizing agent；
S2, the anode sizing agent is coated on plus plate current-collecting body, and carries out drying and processing and forms anode pole piece；
S3, the anode pole piece and matched cathode pole piece, diaphragm are assembled in battery case, then to battery case
Carry out injection electrolyte for the first time；
S4, after standing specified time under assigned temperature, chemical conversion treatment is carried out；
S5, after the intracorporal gas of the battery case is discharged, second of injection electrolyte is carried out.
Electrode material
The positive electrode of battery uses ternary material.Ternary material is the lithium salts for including nickel, cobalt, manganese, such as Li
(NiCoMn)0.33O2(i.e. Li3NiCoMnO6).Be also possible to comprising nickel, cobalt, aluminium lithium salts, such as NCA.Ternary composite cathode material
Presoma product is using nickel salt, cobalt salt, manganese salt as raw material, and the ratio of the inside nickel cobalt manganese can adjust according to actual needs, ternary
The battery that material does anode is more increased relative to ferric phosphate lithium cell capacity, can be used for automobile power cell.
Positive electrode used in the embodiment of the present invention be one of NCM333, NCM523, NCM622, NCM811, NCA or
Any several mixture of person.But it is not limited to above-mentioned material, any anode comprising nickel element inhibits production gas method that should all regard
For within protection scope of the present invention.
Electrolyte composition
Ethylene carbonate (EC): molecular formula: C3H4O3。
Clear colorless liquid (> 35 DEG C) is crystalline solid when room temperature.Boiling point: 248 DEG C/760mmHg, 243-244 DEG C/
740mmHg；Flash-point: 160 DEG C；Density: 1.3218；Index of refraction: 1.4158 (50 DEG C)；Fusing point: 35-38 DEG C；This product is polypropylene
The good solvent of nitrile, polyvinyl chloride.It can be used as the liquid that reels off raw silk from cocoons in weaving；It directly as the solvent for removing sour gas and can also mix
Coagulate the additive of soil；It can be used as the component and raw material of pharmacy in medicine；Also act as plastics blowing agent and synthetic lubricant fluid
Stabilizer.
Propene carbonate: molecular formula: C4H6O3。
Colourless odorlessness or light yellow transparent liquid, are dissolved in water and carbon tetrachloride, and with ether, acetone, benzene etc. is miscible.It is
A kind of excellent polar solvent.This product is mainly used for high score subjob, gas separating technology and electrochemistry.Especially it is used to inhale
Natural gas, petrochemical plant synthetic ammonia feedstock carbon dioxide therein are received, plasticizer, spin solvent, alkene and aromatic hydrocarbons extraction are also acted as
Take agent etc..
Diethyl carbonate (DEC): molecular formula: C5H10O3。
Colourless liquid, slightly smell；1.33kPa/23.8 DEG C of vapour pressure；25 DEG C of flash-point；- 43 DEG C of fusing point；Boiling point 125.8
℃；Dissolubility: it is not soluble in water, it is miscible in most organic solvents such as alcohol, ketone, ester；Density: relative density (water=1) 1.0；Phase
To density (air=1) 4.07；Stability: stablize；Risk markings 7 (flammable liquid).
Dimethyl carbonate (dimethyl carbonate, DMC), C3H6O3。
Dimethyl carbonate is a kind of industrial chemicals nontoxic, environmental-protecting performance is excellent, widely used, it, which is that one kind is important, has
Machine synthetic intermediate has a variety of reactivity worth, is producing containing functional groups such as carbonyl, methyl and methoxyl groups in molecular structure
In have the characteristics that using conveniently, safely, pollution less, be easy transport.It is a kind of with hair since dimethyl carbonate toxicity is smaller
" green " chemical products of exhibition prospect.
DMC have excellent solubility property, melt, boiling spread it is narrow, surface tension is big, and viscosity is low, medium circle electric constant
It is small, while evaporating temperature with higher and faster evaporation rate.DMC not only small toxicity, also has that flash-point is high, steam forces down
It therefore is the green solvent for integrating spatter property and safety with the features such as lower explosion limit is high in air.
Methyl ethyl carbonate (EMC)
Molecular weight: 104.1, density 1.00g/cm3, colourless transparent liquid, 109 DEG C of boiling point, -55 DEG C of fusing point, be in recent years
The chemical products of the high-tech of rise, high added value, a kind of solvent of excellent lithium-ion battery electrolytes, is with carbonic acid two
The last word that methyl esters and lithium ion battery yield increase and extends has carbonic acid concurrently since it possesses methyl and ethyl simultaneously
Dimethyl ester, diethyl carbonate characteristic, and the solvent of extraordinary fragrance and intermediate.
Lithium hexafluoro phosphate
White crystals or powder, relative density 1.50.Hygroscopy is strong；It is soluble easily in water, be also dissolved in low concentration methanol, ethyl alcohol,
The organic solvents such as acetone, carbonates.It is decomposed in exposure air or when heating.Lithium hexafluoro phosphate exists in exposure air or when heating
It is decomposed rapidly in air due to the effect of vapor, releases PF5 and generate white smoke.
EC+DMC, EC+DEC, EC+DMC+EMC, EC+DMC+DEC etc. can be used in common electrolyte system.Electrolyte can
Use the LiPF6 solution of 1mol/L (solvent is above-mentioned any one organic solvent or more than one mixture).
Inhibit to produce gas additive
It can be selected PS (propylene sulfite), in PST (propenyl-1,3-sulfonic acid lactone), VEC (sour vinylethylene)
One or more kinds of mixtures.
PS, molecular formula C3H6O3S, English entitled 1,3,2-Dioxathiane2-oxide.Density 1.347g/mL (25
℃).No. CAS is 4176-55-0.
PST, molecular formula: C3H4O3S, molecular weight: 120.13.82-83 DEG C of fusing point, 257 DEG C of boiling point, density 1.508g/cm3,
109 DEG C of flash-point.No. CAS: 21806-61-1.
VEC, No. CAS: 4427-96-7, molecular formula: C5H6O3, molecular weight: 114.1.237 DEG C of boiling point, 733mmHg
(lit.).Density 1.188g/mL, 25 DEG C (lit.).206 °F of flash-point.
It is the process flow diagram of one embodiment of the invention referring to Fig. 2, Fig. 2.It will inhibit to produce the addition of gas additive first
It in positive electrode, is adequately mixed, obtains anode sizing agent.Above-mentioned positive electrode include ternary active substance, as NCM333,
One of NCM523, NCM622, NCM811, NCA are several.The anode sizing agent is coated on plus plate current-collecting body.
Plus plate current-collecting body generally uses aluminium foil, therefore can be described as coated substrate again.The general technology process of coating includes applying
Cloth substrate (metal foil) is released by unwinding device, feeds coating machine.The head and the tail of substrate are after splicer connects into continuous band by drawing
Sheet devices are sent into tension adjusting device and automatic deviation rectifying device, enter coating dress after being adjusted sheet path tension and sheet path position
It sets.Pole piece slurry is coated in apparatus for coating by predetermined coating weight and space length segmentation.Wet pole piece after coating is sent into dry
Dry road is dried, and drying temperature is set according to coating speed and coating thickness.Currently preferred temperature range be 100~
120℃.It is not volatile since the inhibition production gas additive boiling point of addition provided by the invention is higher, and stability is good.The present invention
At a temperature of using, it can prevent from inhibiting to produce the failure of gas additive.The anode pole piece obtained after drying is entangled through tension adjustment and automatically
It is to the rear to be wound, it is assemblied in battery case with matched cathode pole piece, diaphragm.
When filling electrolyte for the first time in battery case, the amount satisfaction of the electrolyte of injection is able to achieve Battery formation i.e.
It can.Reservoir quantity is calculated generally by capacity, i.e. guarantor's liquid coefficient, protects liquid coefficient=electrolyte content (g)/capacity (A), nickelic
The normal liquid coefficient of protecting of power battery chemical conversion is 2.7~3.5.In the present invention, guarantor's liquid coefficient of injection are as follows: 1.8~2.5.If by changing
It is calculated at injecting electrolytic solution quality/positive electrode quality ratio, value is 0.44~0.57, this is added for total electrolyte
Amount.The mass ratio of electrolyte and positive electrode that the present invention is added before chemical conversion are as follows: 0.3~0.4.The present invention to the greatest extent may be used before chemical conversion
The injection that can be reduced electrolyte reduces and inhibits to produce the effect between gas additive and electrolyte.
Then, battery case stands 0.5~5h under 55~70 DEG C of atmosphere.Preferred temperature is selected as 60 DEG C.It stands
Step can guarantee infiltration of the electrolyte to positive electrode, while the inhibition for also reducing addition produces gas additive and dissolves in electrolyte.
After standing, battery case is again through chemical conversion treatment.After chemical conversion treatment, a certain amount of gas can be generated in battery case
Body.It is excluding the intracorporal gas of battery case and then is supplementing electrolyte, the amount of addition and the matter of positive electrode in battery case
Measure ratio are as follows: 0.15~0.2.
The battery for having supplemented electrolyte is packaged, final lithium battery product is obtained.Traditional performance test side is used again
Method characterizes the performance of lithium battery product.
Example one:
Positive electrode is NCM523, and the PS that quality is positive quality of materials 0.5% is added in experimental group in stirring, according to upper
It states process flow and 2Ah soft-package battery is made, operating voltage is 2.8~4.4V.Herein, positive electrode quality only refers to ternary active
The quality of substance, without including that anode needs other auxiliary agents to be added.Blank group not doping, and routinely process.
Example two:
Positive electrode is NCM523, and the PST that quality is positive quality of materials 0.5% is added in experimental group in stirring, according to
2Ah soft-package battery is made in above-mentioned process flow, and operating voltage is 2.8~4.4V.Herein, positive electrode quality only refers to that ternary is living
Property substance quality, without including that anode needs other auxiliary agents to be added.Blank group not doping, and routinely at technique
Reason.
Example three:
Positive electrode is NCM622, and the PS that quality is positive quality of materials 0.5% is added in experimental group in stirring, according to upper
It states process flow and 2Ah soft-package battery is made, operating voltage is 2.8~4.2V.Herein, positive electrode quality only refers to ternary active
The quality of substance, without including that anode needs other auxiliary agents to be added.Blank group not doping, and routinely process.
Example four:
Positive electrode is NCM622, and the PS that quality is positive quality of materials 0.5% is added in experimental group in stirring, according to upper
It states process flow and 2Ah soft-package battery is made, operating voltage is 2.8~4.2V.Herein, positive electrode quality only refers to ternary active
The quality of substance, without including that anode needs other auxiliary agents to be added.The PS of equal quality, and routinely technique is added in blank group
Processing.
Experiment effect is as follows:
As shown above, propose the method for reducing the high temperature storage production gas of just extremely high-nickel material battery to lithium through the present invention
Battery is handled, and 60 DEG C of storages, 1 year cubical expansivity of experimental group has dropped 47.13% in example one, is tested in example two
60 DEG C of storages, 1 year cubical expansivity of group has dropped 63.22%, 60 DEG C of storages, 1 year cubical expansivity of experimental group in example three
Have dropped 59.54%.And other property retentions are constant, and it is high to illustrate that method proposed by the present invention can efficiently solve positive nickel material
Gentle storage produces gas problem, is greatly lowered expansion rate.
In example four, routinely technique directly adds inhibition and produces gas additive, although can also reduce lithium battery expansion rate,
But it is serious to analyse lithium, and high temperature discharge performance (45 DEG C of 500 circle electric discharges of circulation) greatly declines, hence it is evident that is unsatisfactory for the need of actual product
It wants.And use process provided by the invention, then the problem of analysis lithium is serious, and high temperature discharge performance declines can be eliminated, ensure that
The quality of lithium battery.
Just extremely high-nickel material battery high-temperature stores the method for producing gas for reduction proposed by the present invention, passes through and improves anode
Generation technique, improve high-nickel material high temperature storage when produce gas the problem of；The inhibition that is added produce gas additive only anode at
Film, reduction are lost on cathode, improve the utilization rate of additive；It is only added in anode sizing agent mix stages and inhibits to produce gas addition
The case where agent both reduces the usage amount for inhibiting to produce gas additive, also mitigates anode analysis lithium；It also achieves simultaneously and improves lithium electricity
The target of the gram volume of pond anode.
The above description is only a preferred embodiment of the present invention, is not intended to limit the scope of the invention, all utilizations
Equivalent structure or equivalent flow shift made by description of the invention is applied directly or indirectly in other relevant technology necks
Domain is included within the scope of the present invention.
Claims (8)
1. a kind of method for reducing nickelic battery high-temperature storage and producing gas, which comprises the following steps:
By positive electrode and inhibit to produce the mixing of gas additive, obtains anode sizing agent；
The anode sizing agent is coated on plus plate current-collecting body, and carries out drying and processing and forms anode pole piece；
By the anode pole piece and matched cathode pole piece, diaphragm assembly in battery case, the then is carried out to battery case
Primary injection electrolyte；
After standing specified time under assigned temperature, chemical conversion treatment is carried out；
After the intracorporal gas discharge of the battery case, second of injection electrolyte is carried out；
It is described to inhibit to produce gas additive to include the several mixture of one of PS, PST, VEC or any,
Wherein, PS refers to that propylene sulfite, PST refer to that 1,3- acrylic-sultones, VEC refer to sour vinylethylene.
2. the method according to claim 1 for reducing nickelic battery high-temperature storage and producing gas, which is characterized in that the anode material
Material includes one of NCM333, NCM523, NCM622, NCM811, NCA or any several mixture.
3. the method according to claim 1 for reducing nickelic battery high-temperature storage and producing gas, which is characterized in that the inhibition produces
The additive amount of gas additive is the 0.1%~3% of positive quality of materials.
4. the method according to claim 1 for reducing nickelic battery high-temperature storage and producing gas, which is characterized in that the first time
In the step of injecting electrolyte, the amount of first time electrolyte injection is the 0.3~0.4 of the quality of positive electrode.
5. the method according to claim 1 for reducing nickelic battery high-temperature storage and producing gas, which is characterized in that when described specified
Between be 0.5~5h.
6. the method according to claim 1 for reducing nickelic battery high-temperature storage and producing gas, which is characterized in that described to be dried
Dry-cure is formed in anode pole piece step, and drying temperature is 100~120 DEG C.
7. the method according to claim 1 for reducing nickelic battery high-temperature storage and producing gas, which is characterized in that the specified temperature
Degree is between 55~70 DEG C.
8. the method according to claim 1 for reducing nickelic battery high-temperature storage and producing gas, which is characterized in that described second
Inject electrolyte the step of in, be added electrolyte amount be positive electrode quality 0.15~0.2.
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| CN108695487B (en) * | 2017-04-07 | 2021-09-21 | 宁德时代新能源科技股份有限公司 | Positive plate and energy storage device |
| CN108417770B (en) * | 2018-01-15 | 2021-04-20 | 江西安驰新能源科技有限公司 | Charging and discharging type liquid injection process of lithium ion battery |
| CN110112462A (en) * | 2019-05-20 | 2019-08-09 | 河南省法恩莱特新能源科技有限公司 | A kind of electrolyte and preparation method thereof for improving nickelic 811 material at high temperature circulation and producing gas |
| CN111628218B (en) * | 2020-05-18 | 2021-08-31 | 珠海冠宇电池股份有限公司 | Lithium ion battery and preparation method thereof |
| CN114583260B (en) * | 2022-03-09 | 2023-09-12 | 蜂巢能源科技股份有限公司 | Lithium ion battery electrolyte, liquid injection method and lithium ion battery |
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| CN102082292A (en) * | 2010-12-24 | 2011-06-01 | 西安瑟福能源科技有限公司 | High-temperature lithium ion battery electrolyte and lithium ion battery |
| CN105514417A (en) * | 2016-01-28 | 2016-04-20 | 先进储能材料国家工程研究中心有限责任公司 | High-safety lithium ion battery cathode paste and preparation method thereof |
| CN106410282A (en) * | 2016-10-19 | 2017-02-15 | 广州天赐高新材料股份有限公司 | Pretreatment agent and pretreatment method for high-nickel positive electrode of power lithium ion battery |
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| CN102082292A (en) * | 2010-12-24 | 2011-06-01 | 西安瑟福能源科技有限公司 | High-temperature lithium ion battery electrolyte and lithium ion battery |
| CN105514417A (en) * | 2016-01-28 | 2016-04-20 | 先进储能材料国家工程研究中心有限责任公司 | High-safety lithium ion battery cathode paste and preparation method thereof |
| CN106410282A (en) * | 2016-10-19 | 2017-02-15 | 广州天赐高新材料股份有限公司 | Pretreatment agent and pretreatment method for high-nickel positive electrode of power lithium ion battery |
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