CN107256980A - A kind of method for improving the resistance to over-discharge property of lithium ion battery - Google Patents
A kind of method for improving the resistance to over-discharge property of lithium ion battery Download PDFInfo
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- CN107256980A CN107256980A CN201710586267.7A CN201710586267A CN107256980A CN 107256980 A CN107256980 A CN 107256980A CN 201710586267 A CN201710586267 A CN 201710586267A CN 107256980 A CN107256980 A CN 107256980A
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- Prior art keywords
- lithium ion
- ion battery
- battery
- liodfb
- lithium
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Links
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 61
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 238000000034 method Methods 0.000 title claims abstract description 32
- 239000003792 electrolyte Substances 0.000 claims abstract description 58
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 30
- -1 nitrile compound Chemical class 0.000 claims abstract description 23
- 230000005518 electrochemistry Effects 0.000 claims abstract description 10
- IAHFWCOBPZCAEA-UHFFFAOYSA-N succinonitrile Chemical compound N#CCCC#N IAHFWCOBPZCAEA-UHFFFAOYSA-N 0.000 claims description 19
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 7
- 150000002825 nitriles Chemical class 0.000 claims description 7
- FSTPMFASNVISBU-UHFFFAOYSA-N 2-methoxybenzonitrile Chemical compound COC1=CC=CC=C1C#N FSTPMFASNVISBU-UHFFFAOYSA-N 0.000 claims description 3
- 229910000733 Li alloy Inorganic materials 0.000 claims description 3
- RFFFKMOABOFIDF-UHFFFAOYSA-N Pentanenitrile Chemical compound CCCCC#N RFFFKMOABOFIDF-UHFFFAOYSA-N 0.000 claims description 3
- BTGRAWJCKBQKAO-UHFFFAOYSA-N adiponitrile Chemical compound N#CCCCCC#N BTGRAWJCKBQKAO-UHFFFAOYSA-N 0.000 claims description 3
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 claims description 3
- ZTOMUSMDRMJOTH-UHFFFAOYSA-N glutaronitrile Chemical compound N#CCCCC#N ZTOMUSMDRMJOTH-UHFFFAOYSA-N 0.000 claims description 3
- 239000001989 lithium alloy Substances 0.000 claims description 3
- CUONGYYJJVDODC-UHFFFAOYSA-N malononitrile Chemical compound N#CCC#N CUONGYYJJVDODC-UHFFFAOYSA-N 0.000 claims description 3
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 claims description 3
- 238000003860 storage Methods 0.000 abstract description 28
- 239000007787 solid Substances 0.000 abstract description 26
- 239000002931 mesocarbon microbead Substances 0.000 description 41
- 230000000052 comparative effect Effects 0.000 description 30
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 20
- 229910052802 copper Inorganic materials 0.000 description 18
- 239000010949 copper Substances 0.000 description 18
- 230000004044 response Effects 0.000 description 17
- 229910032387 LiCoO2 Inorganic materials 0.000 description 10
- 238000000354 decomposition reaction Methods 0.000 description 10
- 230000009467 reduction Effects 0.000 description 7
- 238000006722 reduction reaction Methods 0.000 description 7
- 239000000654 additive Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 230000005611 electricity Effects 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 210000004027 cell Anatomy 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 238000010668 complexation reaction Methods 0.000 description 4
- 239000011258 core-shell material Substances 0.000 description 4
- 238000005868 electrolysis reaction Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 229910003002 lithium salt Inorganic materials 0.000 description 4
- 159000000002 lithium salts Chemical class 0.000 description 4
- 239000007774 positive electrode material Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- 229910001290 LiPF6 Inorganic materials 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 239000005030 aluminium foil Substances 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 150000005676 cyclic carbonates Chemical class 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000006056 electrooxidation reaction Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000001629 suppression Effects 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 229910002986 Li4Ti5O12 Inorganic materials 0.000 description 1
- 229910010941 LiFSI Inorganic materials 0.000 description 1
- 229910052493 LiFePO4 Inorganic materials 0.000 description 1
- 229910002995 LiNi0.8Co0.15Al0.05O2 Inorganic materials 0.000 description 1
- 229910001228 Li[Ni1/3Co1/3Mn1/3]O2 (NCM 111) Inorganic materials 0.000 description 1
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 229960002645 boric acid Drugs 0.000 description 1
- 235000010338 boric acid Nutrition 0.000 description 1
- 239000003575 carbonaceous material Substances 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
- 239000000470 constituent Substances 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 230000001550 time effect Effects 0.000 description 1
- 239000002341 toxic gas Substances 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
- H01M10/052—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
- H01M10/05—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
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
-
- 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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4242—Regeneration of electrolyte or reactants
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Secondary Cells (AREA)
Abstract
The invention discloses a kind of method for improving the resistance to over-discharge property of lithium ion battery, methods described comprises the following steps：First, surface electrochemistry is carried out to the negative pole of lithium ion battery into membranization processing using the solution containing LiODFB and nitrile compound, or carries out surface electrochemistry into membranization and internal embedding lithiumation processing；2nd, using the negative pole after step one membranae praeformativa, or using the negative pole assembling lithium ion battery after step one membranae praeformativa and pre- embedding lithium, and while adding LiODFB and nitrile compound in the electrolyte of lithium ion battery.The resistance to overdischarge method of the present invention has taken into account the stability of negative pole solid/electrolyte interface film and negative current collector long-time in high potential of battery, therefore the zero volt storage performance of lithium ion battery can be improved, that is, improves the ability that lithium ion battery tolerance is in zero voltage conditions for a long time.
Description
Technical field
The invention belongs to technical field of lithium ion, it is related to a kind of side for improving the resistance to over-discharge property of lithium ion battery
Method.
Background technology
Voltage is reduced during battery discharge, reaches that nominal discharge blanking voltage just stops electric discharge when normally using, if also continuing to
Electric discharge, as overdischarge.During battery over-discharge to specific voltage, protection circuit can disconnect battery and load, prevent cell voltage
Further reduction.With time lengthening, even if battery and load disconnect, still can gradually self discharge is to harmful low-voltage, even
Zero volt is reached, and is in zero voltage conditions for a long time.This makes capacity of lithium ion battery reduction, cyclical stability deteriorate, or even cause
The security incidents such as inflatable, short circuit.Therefore, lithium ion battery needs to be resistant to the ability for being in zero voltage conditions for a long time.
Lithium ion battery, may be due to the manufacturing defect such as internal short-circuit, outside heated or punching in storage and transportation
The fortuitous event such as hit to overheat, trigger Series Internal exothermic auxiliary reaction, and then cause thermal runaway, occur fire, blast and poison
Gas discharges.By battery discharge to zero volt, that is, after the energy of a charge for emptying battery, then stored and transported, can effectively suppress heat
Security risk out of control.Therefore, lithium ion battery needs excellent zero volt storage performance.Lithium ion battery zero volt storage performance is
It is the ability that tolerance is in zero voltage conditions for a long time.
During lithium ion battery initial charge, negative pole potential drop is low, and in negative terminal surface reduction or decomposition reaction occur for electrolyte,
Product is in negative terminal surface formation solid/electrolyte interface film, and this can irreversibly consume the Li that part is deviate from from positive pole+, then
Discharge process in from negative pole deviate from Li+It is not enough to take the embedding lithium position of positive pole.During overdischarge, as the Li in negative pole+All abjections
When, its current potential can rapid increase, now positive pole be still in not embedding full state, current potential fall is smaller, it is final the two
Discharge curve meets at high potential.The cell voltage of both positive and negative polarity discharge curve intersection is zero, and current potential is referred to as no-voltage electricity at this
Position.Higher zero voltage potential causes solid/electrolyte interface film of negative pole to decompose copper or nickel the collector dissolving with negative pole.
After the solid of negative pole/electrolyte interface film is decomposed, the interfacial film can be re-formed when being charged again to battery, can not
The charge/discharge capacity of battery is consumed inversely.Thickening phenomenon occurs in the solid that negative pole is re-formed/electrolyte interface film, makes battery
Impedance increases；And the solid/electrolyte interface film is persistently thickened in follow-up normal charge and discharge process, causes the cyclicity of battery
It can degenerate.The decomposition of negative pole solid/electrolyte interface film can also produce gas, trigger battery inflatable.
After negative current collector dissolving, the adhesive force of active material and collector is reduced and come off, and causes battery capacity to lose.
Collector can cause open circuit with the dissolving of lug junction seriously.The collector metal ion of dissolving, which is reduced, is deposited on electrode table
Face, hinders Li+Deintercalation；Metallic dendrite puncture barrier film can also even be formed and cause short circuit.
The method for improving negative pole tolerance high potential ability at present is to improve the resistance to electrochemical corrosion energy of negative current collector,
Such as use under high potential stable titanium foil as negative current collector, use nitrile compound copper or nickel collection liquid surface by with
React film forming to suppress the dissolving of collector under high potential etc. in position.But, improve negative pole solid/electrolyte interface film for a long time
The method of tolerance high potential ability there is no report.Being capable of negative pole solid/electrolysis under long-time stable high potential accordingly, it would be desirable to develop
The new method of matter interfacial film, and cooperate with using the method for improving negative current collector resistance to electrochemical corrosion energy, to significantly improve electricity
The zero volt storage performance in pond, i.e., tolerance is in the ability of zero voltage conditions for a long time.
The content of the invention
It is an object of the invention to provide a kind of method for improving the resistance to over-discharge property of lithium ion battery, this method has taken into account institute
Negative pole solid/electrolyte interface the film and negative current collector for stating battery are in the stability of high potential for a long time, therefore can carry
The zero volt storage performance of the high battery, that is, improve battery ability of the tolerance in zero voltage conditions for a long time.
The purpose of the present invention is achieved through the following technical solutions：
A kind of method for improving the resistance to over-discharge property of lithium ion battery, including the following two kinds technical scheme：
Technical scheme one：
First, using containing difluorine oxalic acid boracic acid lithium（LiODFB）Table is carried out to the negative pole of lithium ion battery with the solution of nitrile compound
Face electrochemical filmingization processing；
2nd, lithium ion battery is assembled using the negative pole after step one membranae praeformativa, and in lithium ion battery basic electrolyte simultaneously
Add LiODFB and nitrile compound.
Technical scheme two：
First, surface electrochemistry is carried out to the negative pole of lithium ion battery at membranization using the solution containing LiODFB and nitrile compound
Reason and the embedding lithiumation processing of material internal；
2nd, lithium ion battery is assembled using the negative pole after step one membranae praeformativa and pre- embedding lithium, and in the electrolyte of lithium ion battery
In add LiODFB and nitrile compound simultaneously.
In the present invention, the nitrile compound be acetonitrile, propionitrile, butyronitrile, valeronitrile, own nitrile, malononitrile, succinonitrile, glutaronitrile,
One or more in the materials containing itrile group such as adiponitrile, anisole nitrile.
In the present invention, in the electrochemistry preformation membranization processing procedure, using negative pole as working electrode, when current potential is raised
The lithium, lithium alloy or lithium-containing compound of lithium ion can be deviate from as to electrode, the solution containing LiODFB and nitrile compound is made
For electrolyte, wherein addition LiODFB mass percent is 0.1 ~ 90%, the mass percent of nitrile compound for 0.1 ~
50%, by being discharged to 0 ~ 1.8V vs. Li/Li+Current potential, makes the electrode material and collection liquid surface of negative pole occur electrochemistry
Reaction, forms diaphragm.
In the present invention, inside the negative material embedding lithiumation processing be in the surface electrochemistry into after membranization processing,
Further electric discharge, makes the material internal of the negative pole be embedded in a certain amount of Li+。
In the present invention, the mass percent that LiODFB is added in the electrolyte of the lithium ion battery is 0.1 ~ 10%, nitrile
The mass percent of compound is 0.1 ~ 10%.
When the resistance to overdischarge method of the present invention has taken into account the negative pole solid/electrolyte interface film and long negative current collector of battery
Between be in the stability of high potential, therefore the zero volt storage performance of lithium ion battery can be improved, that is, improve lithium ion battery resistance to
The ability of zero voltage conditions is in by long-time.
Brief description of the drawings
Fig. 1 is the cycle performance curve after the storage of battery zero volt in comparative example 4 and embodiment 1；
Fig. 2 is the cycle performance curve after the storage of battery zero volt in comparative example 6 and embodiment 2.
Embodiment
Technical scheme is further described below in conjunction with the accompanying drawings, but is not limited thereto, it is every to this
Inventive technique scheme is modified or equivalent substitution, without departing from the spirit and scope of technical solution of the present invention, all should be covered
In protection scope of the present invention.
The invention provides a kind of method for improving the resistance to over-discharge property of lithium ion battery, including the following two kinds technical side
Case：
Technical scheme one：
First, surface electrochemistry is carried out to the negative pole of lithium ion battery at membranization using the solution containing LiODFB and nitrile compound
Reason；
2nd, lithium ion battery is assembled into the negative pole after membranization processing using step one, and it is same in the electrolyte of lithium ion battery
Shi Tianjia LiODFB and nitrile compound.
Technical scheme two：
First, surface electrochemistry is carried out to the negative pole of lithium ion battery at membranization using the solution containing LiODFB and nitrile compound
Reason and the embedding lithiumation processing of material internal；
2nd, lithium ion battery is assembled using the negative pole after step one membranae praeformativa and pre- embedding lithium, and in the electrolyte of lithium ion battery
In add LiODFB and nitrile compound simultaneously.
The collector of the applicable lithium ion cell positive of the present invention is aluminium foil, and being coated in the anode constituents on aluminium foil includes
Positive electrode active materials, conductive black and binding agent, wherein：Positive electrode active materials can be LiCoO2、LiMn2O4、LiNi1/3Co1/ 3Mn1/3O2、LiNi0.8Co0.15Al0.05O2、LiFePO4Deng the one or more in positive electrode, but it is not limited to this.With following
For embodiment and comparative example in, positive electrode active materials are with LiCoO2Exemplified by.Positive electrode active materials and conductive black, binding agent
Kynoar（PVDF）Mass ratio with 8:1:Exemplified by 1, but it is not limited thereto suitable for the mass ratio of the present invention.
The collector of the applicable negative electrode of lithium ion battery of the present invention is copper foil, and being coated in the negative pole component on copper foil includes
Negative active core-shell material, conductive black and binding agent, wherein：Negative active core-shell material is carbon material, Li4Ti5O12, metal, alloy, oxygen
One or more in the negative materials such as compound, sulfide, nitride, phosphide and fluoride, but it is not limited to this.With following
For embodiment and comparative example in battery negative active core-shell material with carbonaceous mesophase spherules（MCMB）Exemplified by, negative active core-shell material
With conductive black, PVDF mass ratio with 86:7:Exemplified by 7, but it is not limited thereto suitable for the mass ratio of the present invention.
The basic ingredient of the electrolyte of the applicable lithium ion battery of the present invention includes lithium salts and solvent, wherein：Lithium salts includes
LiPF6、LiBF4、LiClO4, one or more in LiFSI, LiTFSI, but be not limited to this；Solvent includes cyclic carbonate
With linear carbonate etc., cyclic carbonate includes the one or more in ethylene carbonate EC, propene carbonate PC etc., but not office
It is limited to this；Linear carbonate includes one kind or several in dimethyl carbonate DMC, diethyl carbonate DEC, methyl ethyl carbonate EMC etc.
Kind, but it is not limited to this.The lithium salts of the electrolyte of lithium ion battery is with 1mol/L in the embodiment and comparative example that are exemplified below
LiPF6Exemplified by, solvent is by taking the EC and DMC by volume mixed in equal amounts as an example.It is worth noting that, suitable for the lithium of the present invention
The basic lithium salt and base solvent ratio of ion battery electrolyte are not limited thereto.
Comparative example 1：LiCoO2 / MCMB batteries are after the 2.75 ~ 4.2V interval interior normal discharge and recharge of rated voltage, overdischarge
Charge to zero volt and immediately, i.e., storage time is 0 at zero volts.After tested, relative to overdischarge after battery over-discharge
Capacity response rate before is 72.0%.
Comparative example 2：LiCoO2 / MCMB batteries are after the 2.75 ~ 4.2V interval interior normal discharge and recharge of rated voltage, overdischarge
Discharged to zero volt, and to the external 3.9 k Ω of both positive and negative polarity resistance, discharge battery electric quantity and be maintained at zero for a long time
Volt state.After battery zero volt is stored 10 days, then carry out normal discharge and recharge.After tested, relative to zero after the storage of battery zero volt
Capacity response rate before volt storage is 37.6%.
Comparative example 3：LiCoO2 / MCMB batteries are after the 2.75 ~ 4.2V interval interior normal discharge and recharge of rated voltage, overdischarge
To zero volt, and to the external 3.9 k Ω of both positive and negative polarity resistance, discharge battery electric quantity and be maintained at zero voltage conditions for a long time.
After battery zero volt is stored 7 weeks, then carry out normal discharge and recharge.After tested, it is stored relative to zero volt after the storage of battery zero volt
Preceding capacity response rate is 15.7%.
In comparative example 1, comparative example 2 and comparative example 3 battery over-discharge to zero volt or zero volt storage after discharge capacity significantly
Loss, is presented with the increase of zero volt storage time, the rule of capacity response rate reduction.The reason for discharge capacity of the cell loses is to bear
The decomposition of pole solid/electrolyte interface film and the dissolving of negative pole copper current collector.With the increase of zero volt storage time, negative pole solid/electricity
The amount of matter interfacial film decomposition and the amount increase of negative pole copper current collector dissolving are solved, the capacity response rate reduction of battery was reflected and put
The accumulated time effect that electricity is damaged to lithium ion battery.
Comparative example 4：Using MCMB electrodes as working electrode, lithium piece adds 3wt% succinonitrile as to electrode in electrolyte,
It is assembled into battery.To the battery using 2 μ A current discharges to 1.1V, succinonitrile is set to occur on the copper current collector surface of MCMB electrodes
Complexation reaction.The essence of the complexation reaction is that electronegative itrile group is inhaled by the copper ion of copper current collector surface positively charged in electrolyte
Draw, and be deposited on copper current collector surface and form diaphragm, suppress dissolving of the copper current collector under high potential.
Take battery apart afterwards, the MCMB electrodes of membranae praeformativa are taken out, to assemble a new battery.The negative pole of the battery is preformation
The MCMB electrodes of film, extremely just LiCoO23wt% succinonitrile is added in electrode, electrolyte.By the battery 2.75 ~ 4.2V volume
Determine to carry out normal discharge and recharge in voltage range, during which can also occur complexation reaction of the succinonitrile on negative current collector surface, shape
Into diaphragm, suppress dissolving of the copper current collector under high potential.
Next by the battery over-discharge to zero volt, during which negative pole current potential is raised, and can also occur succinonitrile in negative pole currect collecting
The complexation reaction in body surface face, forms diaphragm, suppresses dissolving of the copper current collector under high potential.
To the external 3.9 k Ω of the battery plus-negative plate for being overdisharged to zero volt resistance, make battery electric quantity discharge and it is long when
Between be maintained at zero voltage conditions.After battery zero volt is stored 10 days, then carry out normal discharge and recharge.After tested, battery zero volt stores it
Capacity response rate before being stored afterwards relative to zero volt is 80.5%.
In view of the succinonitrile effect that copper current collector dissolves in the case where negative current collector surface filming has suppression high potential,
Negative pole solid/last decomposition of the electrolyte interface film under high potential when 19.5% capacitance loss is from zero volt storage.
Embodiment 1：Using MCMB electrodes as working electrode, lithium piece is as to electrode, addition 2wt% LiODFB in electrolyte
With 3wt% succinonitrile, battery is assembled into.LiODFB is made in MCMB electrode surfaces to 1.1V using 2 μ A current discharges to the battery
Generation is reduced and decomposition reaction, and product deposits film forming in MCMB electrode surfaces.
The deposition film may stop basic electrode liquid component and the reaction of MCMB electrodes under follow-up low potential, that is, suppress high electricity
The generation of labile Conventional solid/electrolyte interface film under position；Or LiODFB can in the reaction product of MCMB electrode surfaces
Reaction product that can be with follow-up basic electrolyte component in MCMB electrode surfaces produces chemical bonding, so as to obtain steady under high potential
Fixed complex solid/electrolyte interface film.
After MCMB electrode membranae praeformativas, take battery apart and take out MCMB electrodes.A new battery is assembled afterwards, and negative pole is preformation
The MCMB electrodes of film, extremely just LiCoO22wt% LiODFB and 3wt% succinonitrile is added in electrode, electrolyte.The battery exists
In 2.75 ~ 4.2V rated voltage is interval after normal discharge and recharge, zero volt is overdisharged to and to the external 3.9 k Ω's of both positive and negative polarity
Resistance, discharges battery electric quantity and is maintained at zero voltage conditions for a long time.
After battery zero volt is stored 10 days, then carry out normal discharge and recharge.After tested, relative to zero after the storage of battery zero volt
Capacity response rate before volt storage is 98.4%；After electroless solution additive battery zero volt is stored 10 days in comparative example 2
37.6% capacity response rate, is increased dramatically；And the battery zero of succinonitrile is only added apparently higher than electrolyte in comparative example 4
Volt storage 10 days after 80.5% capacity response rate.
The cyclical stability after the battery zero volt of two kinds of additives of LiODFB and succinonitrile is stored 10 days is used in combination to obtain
Good holding.Cycle performance curve after battery zero volt is stored 10 days in comparative example 4 and embodiment 1 is as shown in Figure 2.
After LiODFB and succinonitrile are used in combination, negative pole solid/electrolyte interface film and copper current collector are for a long time in height
The stability of current potential is improved, thus battery zero volt store 10 days after capacity restoration rate close to 100%, and stable circulation
Property keep good.
Comparative example 5：Using MCMB electrodes as working electrode, lithium piece adds 2wt% as to electrode in electrolyte
LiODFB, is assembled into battery.To the battery using 2 μ A current discharges to 1.1V, LiODFB is set to occur also in MCMB electrode surfaces
Former and decomposition reaction, product deposits film forming in MCMB electrode surfaces.
Take battery apart afterwards, the MCMB electrodes of membranae praeformativa are taken out, to assemble a new battery.The negative pole of the battery is preformation
The MCMB electrodes of film, extremely just LiCoO22wt% LiODFB are added in electrode, electrolyte.The battery is in the specified of 2.75 ~ 4.2V
In voltage range after normal discharge and recharge, it is overdisharged to after zero volt and charges immediately, i.e., storage time is 0 at zero volts.
After tested, it is 75.6% relative to the capacity response rate before overdischarge after the battery over-discharge, with comparative example 1
In electroless solution additive battery over-discharge to zero volt after 72.0% capacity response rate it is suitable.This shows to be used alone
LiODFB can not significantly improve the resistance to over-discharge property of battery.Embodiment 1 shows that LiODFB consolidates with negative pole under high potential is stablized
The effect of body/electrolyte interface film, therefore, dissolving of the loss of battery capacity from negative pole copper current collector in comparative example 5.
The succinonitrile effect that copper current collector dissolves in the case where negative current collector surface filming has suppression high potential.According to comparing
Example 4, single succinonitrile does not have the effect for significantly improving negative pole solid/electrolyte interface membrane stability under high potential.According to reality
Example 1 is applied, LiODFB has the effect for stablizing negative pole solid/electrolyte interface film under high potential.According to comparative example 5, it is used alone
LiODFB does not have the effect for significantly inhibiting that copper current collector dissolves under high potential.According to embodiment 1, combination LiODFB and succinonitrile
Afterwards, the stability in high potential is improved for a long time for negative pole solid/electrolyte interface film and copper current collector, therefore battery
Zero volt storage performance be increased dramatically.
Comparative example 6：Using MCMB electrodes as working electrode, lithium piece is free of LiODFB and nitrile as to electrode in electrolyte
Compound, is assembled into battery.By the battery, charge and discharge cycles 10 times in 5mV ~ 2V voltage ranges, make basic electrolyte component exist
Sufficiently reduction and decomposition reaction occur for MCMB electrode surfaces, and product deposits film forming in MCMB electrode surfaces.Then again to battery
Electric discharge, discharge capacity is the reversible capacity of MCMB electrodes 2%, MCMB body phases is embedded in a certain amount of Li in advance+。
Take battery apart afterwards, the MCMB electrodes of membranae praeformativa and pre- embedding lithium are taken out, to assemble new battery.Newly the negative pole of battery is
The MCMB electrodes of membranae praeformativa and pre- embedding lithium, extremely just LiCoO2LiODFB and nitrile compound are free of in electrode, electrolyte.The battery
In 2.75 ~ 4.2V rated voltage is interval after normal discharge and recharge, zero volt is overdisharged to and to the external 3.9 k Ω of both positive and negative polarity
Resistance, make battery electric quantity discharge and for a long time be maintained at zero voltage conditions.After battery zero volt is stored 7 weeks, then normally filled
Electric discharge.
After tested, the capacity response rate before being stored after the storage of battery zero volt relative to zero volt is 70.0%.Comparative example 3
In battery be not used electrolysis additive and not to negative pole carry out membranae praeformativa, zero volt store 7 weeks after capacity response rate be
15.7%.The lifting of capacity response rate derives from negative pole membranae praeformativa and pre- embedding lithium after the storage of battery zero volt in comparative example 6.
After negative pole membranae praeformativa and pre- embedding lithium, battery is reassembled into, the Li of its positive pole abjection+Negative pole can be had fully embedded into
Electrode material body phase, without being lost on the negative pole solid/electrolyte interface film formed；In addition, negative pole body phase also has
Part Li embedded in advance+, this part Li+The positive pole of full lithium state can not be embedded in.
During the battery over-discharge, as the embedding full Li of positive pole+Afterwards, its current potential can rapid decrease；The now Li in negative pole+It is also incomplete
Portion deviates from, therefore the current potential rate of climb is slow, and the discharge curve of final both positive and negative polarity meets at negative pole solid/electrolyte interface film and negative
The metastable low potential of pole collector, so as to improve the resistance to over-discharge property of battery.
The battery zero volt of negative pole membranae praeformativa and pre- embedding lithium still has 30.0% capacitance loss after storing 7 weeks, it may be possible to because with
Zero volt storage time extends, and the zero voltage potential of battery gradually floats height, cause a small amount of negative pole solid/electrolyte interface film decompose and
A small amount of copper current collector dissolving.
Embodiment 2：Using MCMB electrodes as working electrode, lithium piece is as to electrode, addition 2wt% LiODFB in electrolyte
With 3wt% succinonitrile, battery is assembled into.LiODFB is made in MCMB electrode surfaces to 1.1V using 2 μ A current discharges to the battery
Generation is reduced and decomposition reaction, and product deposits film forming in MCMB electrode surfaces.
The deposition film may stop basic electrode liquid component and the reaction of MCMB electrodes under follow-up low potential, that is, suppress high electricity
The generation of labile Conventional solid/electrolyte interface film under position；Or LiODFB can in the reaction product of MCMB electrode surfaces
Reaction product that can be with follow-up basic electrolyte component in MCMB electrode surfaces produces chemical bonding, so as to obtain steady under high potential
Fixed complex solid/electrolyte interface film.
Charge and discharge cycles 10 times in 5mV ~ 2V voltage ranges by the battery, make basic electrolyte component in MCMB electrode tables
Sufficiently reduction and decomposition reaction occur for face, and product deposits film forming in MCMB electrode surfaces.Afterwards again to battery discharge, electric discharge is held
Measure as the reversible capacity of MCMB electrodes 2%, MCMB body phases is embedded in a certain amount of Li in advance+。
Then take battery apart, the MCMB electrodes of membranae praeformativa and pre- embedding lithium are taken out, to assemble new battery.Newly the negative pole of battery is
The MCMB electrodes of membranae praeformativa and pre- embedding lithium, extremely just LiCoO22wt% LiODFB and 3wt% fourth two is added in electrode, electrolyte
Nitrile.
The battery after normal discharge and recharge, is overdisharged to zero volt and to both positive and negative polarity in 2.75 ~ 4.2V rated voltage is interval
External 3.9 k Ω resistance, makes battery electric quantity discharge and for a long time in zero voltage conditions storage.After battery zero volt is stored 7 weeks,
Normal discharge and recharge is carried out again.Capacity response rate before being stored after the storage of battery zero volt relative to zero volt is 98.8%.
Battery in comparative example 6, negative pole has carried out membranae praeformativa and pre-embedding lithium processes, but without two kinds of LiODFB and nitrile compound
Electrolysis additive, the capacity response rate after battery zero volt is stored 7 weeks is 70.0%.LiODFB and succinonitrile are used in embodiment 2
Two kinds of electrolysis additives and the battery for combining pre- embedding lithium, negative pole solid/electrolyte interface film and copper current collector are stored for a long time
When stability be improved, therefore battery zero volt store 7 weeks after capacity restoration rate close to 100%, and cyclical stability is protected
Hold good.Cycle performance curve after battery zero volt is stored 7 weeks in comparative example 6 and embodiment 2 is as shown in Figure 2.
It is electric in comparative example 1, comparative example 2, comparative example 3, comparative example 4, comparative example 5, comparative example 6, embodiment 1 and embodiment 2
Capacity response rate before being stored after the zero volt storage of pond relative to zero volt is as shown in table 1.
Table 1
Claims (8)
1. a kind of method for improving the resistance to over-discharge property of lithium ion battery, it is characterised in that methods described step is as follows：
First, surface electrochemistry is carried out to the negative pole of lithium ion battery at membranization using the solution containing LiODFB and nitrile compound
Reason；
2nd, lithium ion battery is assembled using the negative pole after step one membranae praeformativa, and added simultaneously in the electrolyte of lithium ion battery
Plus LiODFB and nitrile compound.
2. the method according to claim 1 for improving the resistance to over-discharge property of lithium ion battery, it is characterised in that the nitrilation
Compound be acetonitrile, propionitrile, butyronitrile, valeronitrile, own nitrile, malononitrile, succinonitrile, glutaronitrile, adiponitrile, one kind in anisole nitrile or
It is several.
3. the method according to claim 1 for improving the resistance to over-discharge property of lithium ion battery, it is characterised in that the electrification
Study in membranization processing procedure, using negative pole as working electrode, lithium, lithium alloy or lithium-containing compound contain as to electrode
The solution of LiODFB and nitrile compound is as electrolyte, wherein addition LiODFB mass percent is 0.1 ~ 90%, nitrilation is closed
The mass percent of thing is 0.1 ~ 50%, is discharged to 0 ~ 1.8V vs. Li/Li+Current potential.
4. it is according to claim 1 improve the resistance to over-discharge property of lithium ion battery method, it is characterised in that the lithium from
In the electrolyte of sub- battery, addition LiODFB mass percent is 0.1 ~ 10%, and the mass percent of nitrile compound is 0.1
~ 10%。
5. a kind of method for improving the resistance to over-discharge property of lithium ion battery, it is characterised in that methods described step is as follows：
First, surface electrochemistry is carried out to the negative pole of lithium ion battery at membranization using the solution containing LiODFB and nitrile compound
Reason and the embedding lithiumation processing of material internal；
2nd, lithium ion battery is assembled using the negative pole after step one membranae praeformativa and pre- embedding lithium, and in the electrolyte of lithium ion battery
In add LiODFB and nitrile compound simultaneously.
6. the method according to claim 5 for improving the resistance to over-discharge property of lithium ion battery, it is characterised in that the nitrilation
Compound be acetonitrile, propionitrile, butyronitrile, valeronitrile, own nitrile, malononitrile, succinonitrile, glutaronitrile, adiponitrile, one kind in anisole nitrile or
It is several.
7. the method according to claim 5 for improving the resistance to over-discharge property of lithium ion battery, it is characterised in that the electrification
Study in membranization processing procedure, using negative pole as working electrode, lithium, lithium alloy or lithium-containing compound contain as to electrode
The solution of LiODFB and nitrile compound is as electrolyte, wherein addition LiODFB mass percent is 0.1 ~ 90%, nitrilation is closed
The mass percent of thing is 0.1 ~ 50%, is discharged to 0 ~ 1.8V vs. Li/Li+Current potential.
8. it is according to claim 5 improve the resistance to over-discharge property of lithium ion battery method, it is characterised in that the lithium from
In the electrolyte of sub- battery, addition LiODFB mass percent is 0.1 ~ 10%, and the mass percent of nitrile compound is 0.1
~ 10%。
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| CN108717977A (en) * | 2018-05-29 | 2018-10-30 | 哈尔滨工业大学 | A kind of lithium ion battery with excellent zero volt storage performance |
| CN109659500A (en) * | 2018-12-18 | 2019-04-19 | 西北工业大学 | Reduce solid electrolyte/cathode of lithium interface impedance lithium piece, preparation method and application |
| CN111864277A (en) * | 2020-08-20 | 2020-10-30 | 苏州合睿新能源科技有限公司 | Method for manufacturing lithium ion battery capable of resisting storage discharge to zero volt |
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| CN113113573B (en) * | 2021-03-30 | 2022-06-21 | 天能电池集团股份有限公司 | Impregnation liquid for treating negative plate of dry-charged battery, negative plate and battery |
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