CN106340671B - Lithium ion battery and electrolyte thereof - Google Patents
Lithium ion battery and electrolyte thereof Download PDFInfo
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- CN106340671B CN106340671B CN201510396731.7A CN201510396731A CN106340671B CN 106340671 B CN106340671 B CN 106340671B CN 201510396731 A CN201510396731 A CN 201510396731A CN 106340671 B CN106340671 B CN 106340671B
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- ion battery
- lithium
- lithium ion
- additive
- electrolyte
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 132
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 132
- 239000003792 electrolyte Substances 0.000 title claims abstract description 59
- 239000000654 additive Substances 0.000 claims abstract description 56
- 230000000996 additive effect Effects 0.000 claims abstract description 55
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 9
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 9
- 239000011356 non-aqueous organic solvent Substances 0.000 claims abstract description 9
- 238000002955 isolation Methods 0.000 claims description 9
- -1 aromatic radical Chemical class 0.000 claims description 8
- 239000006258 conductive agent Substances 0.000 claims description 8
- YTZKOQUCBOVLHL-UHFFFAOYSA-N tert-butylbenzene Chemical compound CC(C)(C)C1=CC=CC=C1 YTZKOQUCBOVLHL-UHFFFAOYSA-N 0.000 claims description 8
- 239000011230 binding agent Substances 0.000 claims description 7
- HHNHBFLGXIUXCM-GFCCVEGCSA-N cyclohexylbenzene Chemical compound [CH]1CCCC[C@@H]1C1=CC=CC=C1 HHNHBFLGXIUXCM-GFCCVEGCSA-N 0.000 claims description 7
- 239000012528 membrane Substances 0.000 claims description 7
- 239000007774 positive electrode material Substances 0.000 claims description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- 239000007773 negative electrode material Substances 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 4
- 229910052744 lithium Inorganic materials 0.000 claims description 4
- 229910014397 LiNi1/3Co1/3Mn1/3 Inorganic materials 0.000 claims description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- 238000005524 ceramic coating Methods 0.000 claims description 3
- 239000002131 composite material Substances 0.000 claims description 3
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 3
- 125000000524 functional group Chemical group 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 229920000098 polyolefin Polymers 0.000 claims description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 3
- 238000006467 substitution reaction Methods 0.000 claims description 3
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 claims description 2
- QHTJSSMHBLGUHV-UHFFFAOYSA-N 2-methylbutan-2-ylbenzene Chemical compound CCC(C)(C)C1=CC=CC=C1 QHTJSSMHBLGUHV-UHFFFAOYSA-N 0.000 claims description 2
- 229910005271 Li(CoxNiyMn1-x-y)O2 Inorganic materials 0.000 claims description 2
- 229910005273 Li(CoxNiyMn1−x−y)O2 Inorganic materials 0.000 claims description 2
- 229910013188 LiBOB Inorganic materials 0.000 claims description 2
- 229910000552 LiCF3SO3 Inorganic materials 0.000 claims description 2
- 229910032387 LiCoO2 Inorganic materials 0.000 claims description 2
- 229910010941 LiFSI Inorganic materials 0.000 claims description 2
- 229910021447 LiN(CxF2x+1SO2)(CyF2y+1SO2) Inorganic materials 0.000 claims description 2
- 229910001290 LiPF6 Inorganic materials 0.000 claims description 2
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 claims description 2
- LUJAXSNNYBCFEE-UHFFFAOYSA-N Quercetin 3,7-dimethyl ether Natural products C=1C(OC)=CC(O)=C(C(C=2OC)=O)C=1OC=2C1=CC=C(O)C(O)=C1 LUJAXSNNYBCFEE-UHFFFAOYSA-N 0.000 claims description 2
- PUTDIROJWHRSJW-UHFFFAOYSA-N Quercitrin Natural products CC1OC(Oc2cc(cc(O)c2O)C3=CC(=O)c4c(O)cc(O)cc4O3)C(O)C(O)C1O PUTDIROJWHRSJW-UHFFFAOYSA-N 0.000 claims description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 2
- OXGUCUVFOIWWQJ-XIMSSLRFSA-N acanthophorin B Natural products O[C@H]1[C@H](O)[C@H](O)[C@H](C)O[C@H]1OC1=C(C=2C=C(O)C(O)=CC=2)OC2=CC(O)=CC(O)=C2C1=O OXGUCUVFOIWWQJ-XIMSSLRFSA-N 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
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 2
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 claims description 2
- 229910001540 lithium hexafluoroarsenate(V) Inorganic materials 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
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 claims description 2
- 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 claims description 2
- OEKUVLQNKPXSOY-UHFFFAOYSA-N quercetin 3-O-beta-D-glucopyranosyl(1->3)-alpha-L-rhamnopyranosyl(1->6)-beta-d-galactopyranoside Natural products OC1C(O)C(C(O)C)OC1OC1=C(C=2C=C(O)C(O)=CC=2)OC2=CC(O)=CC(O)=C2C1=O OEKUVLQNKPXSOY-UHFFFAOYSA-N 0.000 claims description 2
- QPHXPNUXTNHJOF-UHFFFAOYSA-N quercetin-7-O-beta-L-rhamnopyranoside Natural products OC1C(O)C(O)C(C)OC1OC1=CC(O)=C2C(=O)C(O)=C(C=3C=C(O)C(O)=CC=3)OC2=C1 QPHXPNUXTNHJOF-UHFFFAOYSA-N 0.000 claims description 2
- OXGUCUVFOIWWQJ-HQBVPOQASA-N quercitrin Chemical group O[C@@H]1[C@H](O)[C@@H](O)[C@H](C)O[C@H]1OC1=C(C=2C=C(O)C(O)=CC=2)OC2=CC(O)=CC(O)=C2C1=O OXGUCUVFOIWWQJ-HQBVPOQASA-N 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 125000005586 carbonic acid group Chemical group 0.000 claims 1
- 125000005843 halogen group Chemical group 0.000 claims 1
- 230000002265 prevention Effects 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 41
- REFJWTPEDVJJIY-UHFFFAOYSA-N Quercetin Chemical compound C=1C(O)=CC(O)=C(C(C=2O)=O)C=1OC=2C1=CC=C(O)C(O)=C1 REFJWTPEDVJJIY-UHFFFAOYSA-N 0.000 description 22
- 238000000034 method Methods 0.000 description 13
- 239000000126 substance Substances 0.000 description 13
- 238000012360 testing method Methods 0.000 description 13
- 230000014759 maintenance of location Effects 0.000 description 12
- ZVOLCUVKHLEPEV-UHFFFAOYSA-N Quercetagetin Natural products C1=C(O)C(O)=CC=C1C1=C(O)C(=O)C2=C(O)C(O)=C(O)C=C2O1 ZVOLCUVKHLEPEV-UHFFFAOYSA-N 0.000 description 11
- HWTZYBCRDDUBJY-UHFFFAOYSA-N Rhynchosin Natural products C1=C(O)C(O)=CC=C1C1=C(O)C(=O)C2=CC(O)=C(O)C=C2O1 HWTZYBCRDDUBJY-UHFFFAOYSA-N 0.000 description 11
- MWDZOUNAPSSOEL-UHFFFAOYSA-N kaempferol Natural products OC1=C(C(=O)c2cc(O)cc(O)c2O1)c3ccc(O)cc3 MWDZOUNAPSSOEL-UHFFFAOYSA-N 0.000 description 11
- 229960001285 quercetin Drugs 0.000 description 11
- 235000005875 quercetin Nutrition 0.000 description 11
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 10
- 238000003860 storage Methods 0.000 description 10
- 150000002500 ions Chemical class 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- 235000010290 biphenyl Nutrition 0.000 description 5
- 239000004305 biphenyl Substances 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 230000005611 electricity Effects 0.000 description 5
- 238000011056 performance test Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 230000005713 exacerbation Effects 0.000 description 3
- 230000002427 irreversible effect Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 229910002991 LiNi0.5Co0.2Mn0.3O2 Inorganic materials 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- SOXUFMZTHZXOGC-UHFFFAOYSA-N [Li].[Mn].[Co].[Ni] Chemical compound [Li].[Mn].[Co].[Ni] SOXUFMZTHZXOGC-UHFFFAOYSA-N 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000000593 degrading effect Effects 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000011267 electrode slurry Substances 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 150000002367 halogens Chemical group 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 235000013824 polyphenols Nutrition 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 238000005476 soldering Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000009966 trimming Methods 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 229910001228 Li[Ni1/3Co1/3Mn1/3]O2 (NCM 111) Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- 241001480055 Quercus mongolica Species 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000007767 bonding agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000006713 insertion reaction Methods 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000009783 overcharge test Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 150000004291 polyenes Chemical class 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 230000001568 sexual effect Effects 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 230000001960 triggered effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000004804 winding 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
- H01M10/056—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
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion 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
- 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
Landscapes
- 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 provides a lithium ion battery and electrolyte thereof. The electrolyte of the lithium ion battery comprises lithium salt and a non-aqueous organic solvent. The electrolyte also includes an overcharge prevention additive and an auxiliary film forming additive. The lithium ion battery comprises the lithium ion battery electrolyte. The lithium ion battery effectively solves the problems of increased direct current resistance and deteriorated electrochemical performance of the lithium ion battery caused by the addition of the overcharge-preventing additive, and meanwhile, the lithium ion battery has good overcharge resistance.
Description
Technical field
The present invention relates to battery technology field more particularly to a kind of lithium ion batteries and its electrolyte.
Background technology
Continue charging after lithium ion battery completely fills when there is overcharge, the positive and negative anodes of lithium ion battery can all be in one kind
The state of " excess load ", therefore will produce a series of side reaction.At anode, current potential increases non-in easily oxidation electrolyte
Aqueous organic solvent, and the heat that non-aqueous organic solvent oxidation reaction is discharged caused by overcharge is significantly larger than normal charge and discharge
The heat that oxidation reaction is discharged occurs for non-aqueous organic solvent in the case of electricity；At cathode, the insertion reaction of lithium ion can continue
It carries out, lithium ion is caused to be easy that deposition reaction occurs in negative terminal surface.These abnormal responses can all make the performance of lithium ion battery
The problems such as deteriorating rapidly, large area diffusion, the internal short-circuit of battery of heat can occur when more serious, increases lithium ion battery and rises
Hot fried possibility.
In order to avoid the variety of problems that overcharge is brought, common practice in the art is the electricity in lithium ion battery at present
Added in solution liquid improves the over-charging of lithium ion battery with reversible and irreversible and closing effect additive on a small quantity.
Especially there is the additive for closing effect, do not limited by the diffusion of invertibity additive and concentration, in lithium ion battery
There is wider application.When overcharge occurs for lithium ion battery, voltage rises rapidly, such has the addition for closing effect
Irreversible chemical reaction process occurs for agent, and mainly by generating gas opening current control safety valve cut-out electric current or leading to
It crosses polymerization and increases battery impedance reduction electric current to realize a kind of irreversible, disposable charge cutoff.
When biphenyl, cyclohexyl benzene, tert-butyl benzene etc. are added in electrolyte with the benzene-like compounds for closing effect, energy
It is enough to polymerize at positive electrode in battery overcharge, cause the increase of battery middle impedance, generates the open-top electric current of bulk gas
Control the cut-out that safety valve realizes electric current.But the addition of such additives deteriorates performance of lithium ion battery in serious, direct current
Resistance increases, and storage performance and cycle performance are poor, and sexual when its addition is more than the 2% of the mass percentage of electrolyte
The risk of energy severe exacerbation, therefore the security performance of lithium ion battery and chemical property can not be taken into account.
Invention content
The problem of in view of background technology, the purpose of the present invention is to provide a kind of lithium ion battery and its electrolysis
Liquid, the addition that the lithium ion battery efficiently solves anti-overcharge additive cause lithium ion battery D.C. resistance to increase, are electrochemical
The problem of learning penalty, while the overcharge resistance performance energy that lithium ion battery has had.
To achieve the goals above, in the first aspect of the present invention, the present invention provides a kind of electrolysis of lithium ion battery
Liquid comprising lithium salts and non-aqueous organic solvent.The electrolyte further includes anti-overcharge additive and auxiliary film for additive；
The structural formula of the anti-overcharge additive is as follows：
Wherein, the H on 1,2,3,4,5,6 is replaced by alkyl, naphthenic base, F or phenyl each independently；It is described auxiliary at
The structural formula of film additive is as follows：
Wherein, the H on 3,5,6,7,8,1 ', 2 ', 3 ', 4 ' and 5 ' positions each independently by phenolic hydroxyl group, hydroxyl, alkyl,
Alkoxy, carboxyl, amino, aromatic radical or the above-mentioned functional group of halogen substitution are replaced.
In the second aspect of the present invention, the present invention provides a kind of lithium ion batteries comprising：Anode pole piece, including just
Pole collector and the positive diaphragm for being set on plus plate current-collecting body and include positive electrode active materials, conductive agent and binder；It is negative
Pole pole piece, including negative current collector and be set on negative current collector and include negative electrode active material, conductive agent and binder
Cathode membrane；Isolation film is interval between anode pole piece and cathode pole piece；And electrolyte.Wherein, the electrolyte is root
According to the lithium-ion battery electrolytes described in first aspect present invention.
Compared with the existing technology, beneficial effects of the present invention are as follows：
In the lithium-ion battery electrolytes of the present invention, when lithium ion battery is in overcharging state, anti-overcharge additive
Addition make lithium ion battery under the conditions of overcharging can a large amount of aerogenesis, with open current control safety valve cut-out electric current ensure
The overcharge safety of lithium ion battery.But when lithium ion battery normal use, anti-overcharge additive can be aggregated into anode
Film, and it is finer and close, larger at film resistance to form a film so that electron conduction and ion conduction are poor, are degrading lithium ion battery
Chemical property.And assist the addition of film for additive that can form a film with auxiliary positive, improve the structure of film forming, forms a kind of tool
Have good space structure and electron conduction and the good elastomeric state structure of ion conduction, effectively solve anti-overcharge additive plus
The problem of entering to cause the increase of lithium ion battery D.C. resistance, chemical property to deteriorate is ensureing that it is resistance to that lithium ion battery has had
The chemical property for making lithium ion battery also have while over-charging.
Description of the drawings
Fig. 1 shows the D.C. resistance of comparative example 1 and comparative example 2 under different charged states at 25 DEG C；
Fig. 2 shows capacity retention ratios after the storage of comparative example 1 and comparative example 2 at 60 DEG C；
Fig. 3 shows at 60 DEG C capacity retention ratio after the cycle of comparative example 1 and comparative example 2；
Fig. 4 shows the D.C. resistance of comparative example 4-5 and embodiment 6 under different charged states at 25 DEG C；
Fig. 5 shows the capacity retention ratio after the storage of comparative example 4-5 and embodiment 6 at 60 DEG C；
Fig. 6 shows the capacity retention ratio after the cycle of comparative example 4-5 and embodiment 6 at 60 DEG C.
Specific implementation mode
Illustrate below lithium ion battery and its electrolyte and embodiment according to the present invention, comparative example and test process with
And test result.
Illustrate lithium-ion battery electrolytes according to a first aspect of the present invention first.
Lithium-ion battery electrolytes according to a first aspect of the present invention include lithium salts and non-aqueous organic solvent.The electrolysis
Liquid further includes anti-overcharge additive and auxiliary film for additive；The structural formula of the anti-overcharge additive is as follows：
Wherein, the H on 1,2,3,4,5,6 is replaced by alkyl, naphthenic base, F or phenyl each independently；It is described auxiliary at
The structural formula of film additive is as follows：
Wherein, the H on 3,5,6,7,8,1 ', 2 ', 3 ', 4 ' and 5 ' positions each independently by phenolic hydroxyl group, hydroxyl, alkyl,
Alkoxy, carboxyl, amino, aromatic radical or the above-mentioned functional group of halogen substitution are replaced.
In the lithium-ion battery electrolytes described according to a first aspect of the present invention, when lithium ion battery is in overcharging state
When, the addition of anti-overcharge additive make lithium ion battery under the conditions of overcharging can a large amount of aerogenesis, to open current control peace
Full valve cuts off the overcharge safety that electric current ensures lithium ion battery.But when lithium ion battery normal use, anti-overcharge addition
Agent can be in positive polymerization film formation, and it is finer and close, larger at film resistance to form a film so that and electron conduction and ion conduction are poor,
It is degrading the chemical property of lithium ion battery.And assist the addition of film for additive that can form a film with auxiliary positive, improve film forming
Structure, form a kind of elastomeric state structure good with good space structure and electron conduction and ion conduction, effectively solve
The problem of addition of certainly anti-overcharge additive causes lithium ion battery D.C. resistance to increase, chemical property deteriorates is ensureing lithium
Make lithium ion battery also with good chemical property while ion battery is with good overcharge resistance performance energy.
In the lithium-ion battery electrolytes described according to a first aspect of the present invention, the anti-overcharge additive can be selected from joining
One or more of benzene, cyclohexyl benzene, meta-terphenyl, phenyl-pentafluoride, tert-butyl benzene, tert-amyl benzene and 2- fluorine biphenyl.
In the lithium-ion battery electrolytes described according to a first aspect of the present invention, the anti-overcharge additive is in lithium ion
Mass percentage in battery electrolyte can be 0.5%~8%.The content of anti-overcharge additive is less than 0.5%, and gas production is too
It is not enough to open current control safety valve cut-out electric current less, and then can not ensure the overcharge safety of lithium ion battery；It is anti-overcharge
The content of additive is more than 8%, and aerogenesis is too many, with good chemical property when can not ensure lithium ion battery normal use.
In the lithium-ion battery electrolytes described according to a first aspect of the present invention, the auxiliary film for additive can be Mongolian oak
Pi Su, structural formula are as follows：
In the lithium-ion battery electrolytes described according to a first aspect of the present invention, the auxiliary film for additive lithium from
Mass percentage in sub- battery electrolyte can be 0.002%~0.1%.The content of auxiliary film for additive is less than
0.002%, then its free radical absorption potential must be weaker, is not enough to lithium ion battery caused by the addition for making up anti-overcharge additive
It can deterioration problem；The content of film for additive is assisted to be more than 0.1%, since its molecular weight is larger, solubility in the electrolytic solution
Smaller, excessive its of addition cannot be completely dissolved in the electrolytic solution.
In the lithium-ion battery electrolytes described according to a first aspect of the present invention, the non-aqueous organic solvent can be selected from carbon
One or more of vinyl acetate, propene carbonate, dimethyl carbonate, diethyl carbonate and methyl ethyl carbonate.
In the lithium-ion battery electrolytes described according to a first aspect of the present invention, the lithium salts can be selected from LiTFSI,
LiFSI、LiN(CxF2x+1SO2)(CyF2y+1SO2)、LiPF6、LiBF4、LiBOB、LiAsF6、LiCF3SO3And LiClO4In one
Kind is several, and wherein x, y are natural number.
In the lithium-ion battery electrolytes described according to a first aspect of the present invention, the concentration of lithium salts can be 0.8mol/L~
1.5mol/L。
Secondly the lithium ion battery of explanation according to a second aspect of the present invention.
Lithium ion battery according to a second aspect of the present invention, including：Anode pole piece, including plus plate current-collecting body and be set to just
On the collector of pole and include positive electrode active materials, conductive agent and binder positive diaphragm；Cathode pole piece, including negative pole currect collecting
Body and the cathode membrane for being set on negative current collector and include negative electrode active material, conductive agent and binder；Isolation film,
Every between anode pole piece and cathode pole piece；And electrolyte.Wherein, the electrolyte is according to described in first aspect present invention
Lithium-ion battery electrolytes.
In the lithium ion battery described according to a second aspect of the present invention, the positive electrode active materials can be selected from LiCoO2、
LiMn2O4、LiNi1/3Co1/3Mn1/3And Li (CoxNiyMn1-x-y)O2One or more of, wherein 0.3≤x≤0.8,0.1
≤ y≤0.4,0.6≤x+y≤0.9.
In the lithium ion battery described according to a second aspect of the present invention, the negative electrode active material can be selected from graphite and/
Or silicon.
In the lithium ion battery described according to a second aspect of the present invention, isolation film can be selected from polyolefin film and polyene
One or more of hydrocarbon/ceramic coating composite membrane.
The comparative example and embodiment of lithium ion battery and its electrolyte according to the present invention will be illustrated next.
Comparative example 1
(1) preparation of anode pole piece：By positive electrode active materials lithium nickel cobalt manganese LiNi1/3Co1/3Mn1/3, conductive agent Super P
And binder polyvinylidene fluoride (PVDF) in mass ratio 97:2:1 is made just with solvent N-methyl pyrilidone (NMP) mixing
Anode sizing agent is uniformly coated in current collector aluminum foil and is cold-pressed after being dried at 85 DEG C, then carried out by pole slurry later
After trimming, cut-parts, slitting, then 4h is dried under 85 DEG C of vacuum condition, soldering polar ear completes the preparation of anode pole piece.
(2) preparation of cathode pole piece：By negative electrode active material graphite, conductive agent Super P, thickener CMC and bonding
Agent agent SBR in mass ratio 97:1:1:1 is made negative electrode slurry with solvent deionized water mixing, later by negative electrode slurry even spread
It is cold-pressed after being dried on copper foil of affluxion body and at 85 DEG C, after then carrying out trimming, cut-parts, slitting, then in 110 DEG C of vacuum
Under the conditions of dry 4h, soldering polar ear completes the preparation of cathode pole piece.
(3) preparation of electrolyte：Electrolyte is with the LiPF of a concentration of 1mol/L6For lithium salts, with ethylene carbonate (EC), carbon
The mixture of sour methyl ethyl ester (EMC) and diethyl carbonate (DEC) is non-aqueous organic solvent, and the mass ratio of EC, EMC, DMC are 30:
50:20。
(4) preparation of lithium ion battery：Using polypropylene film as isolation film, by anode pole piece obtained, isolation film, bear
Pole pole piece is folded in order, and isolation film is made to be among positive and negative anodes pole piece, and winding obtains naked battery core；Naked battery core is placed in outside battery core
In packaging, electrolyte, encapsulation, standing, chemical conversion, shaping, volume test are injected later, completes the preparation of lithium ion battery, wherein
The thickness of lithium ion battery is 4.2mm, width 32mm, length 82mm.
Comparative example 2
Prepare lithium ion battery with reference to the method for comparative example 1, unlike add mass percentage in electrolyte and be
0.005% auxiliary film for additive Quercetin.
Comparative example 3
Prepare lithium ion battery with reference to the method for comparative example 1, unlike add mass percentage in electrolyte and be
2% anti-overcharge additive biphenyl.
Comparative example 4
Lithium ion battery is prepared with reference to the method for comparative example 1, the difference is that positive electrode active materials are lithium nickel cobalt manganese
LiNi0.5Co0.2Mn0.3O2。
Comparative example 5
Prepare lithium ion battery with reference to the method for comparative example 4, unlike add mass percentage in electrolyte and be
3% cyclohexyl benzene.
Embodiment 1
Prepare lithium ion battery with reference to the method for comparative example 1, unlike add mass percentage in electrolyte and be
2% anti-overcharge additive biphenyl and 0.005% auxiliary film for additive Quercetin.
Embodiment 2
Prepare lithium ion battery with reference to the method for comparative example 1, unlike add mass percentage in electrolyte and be
2% anti-overcharge additive biphenyl and 0.008% auxiliary film for additive Quercetin.
Embodiment 3
Prepare lithium ion battery with reference to the method for comparative example 1, unlike add mass percentage in electrolyte and be
2% anti-overcharge additive biphenyl, 1% anti-overcharge additive cyclohexyl benzene and 0.005% auxiliary film for additive quercitrin
Element.
Embodiment 4
Prepare lithium ion battery with reference to the method for comparative example 1, unlike add mass percentage in electrolyte and be
5% tert-butyl benzene and 0.003% auxiliary film for additive Quercetin.
Embodiment 5
Lithium ion battery is prepared with reference to the method for embodiment 1, the difference is that the isolation film used is polypropylene/ceramic coating
Composite membrane.
Embodiment 6
Prepare lithium ion battery with reference to the method for comparative example 4, unlike add mass percentage in electrolyte and be
3% cyclohexyl benzene and 0.005% auxiliary film for additive Quercetin.
Embodiment 7
Prepare lithium ion battery with reference to the method for comparative example 4, unlike add mass percentage in electrolyte and be
3% cyclohexyl benzene, 1% anti-overcharge additive 2- fluorine biphenyl and 0.005% auxiliary film for additive Quercetin.
Finally provide the performance test process and test result of the lithium ion battery of comparative example 1-5 and embodiment 1-7.
(1) the aerogenesis volume that overcharges of lithium ion battery is tested
Overcharge gas production whether can be by overcharging the standard of test as measurement lithium ion battery using lithium ion battery, and makes
It is carried out overcharging the test of aerogenesis volume with soft-package battery.At 25 DEG C, first lithium ion battery is charged to the constant current of 1C
4.2V is further less than 0.05C, then by lithium ion battery with the constant current of 0.5C with 4.2V constant-potential charges to electric current
It is discharged to 3.0V, carries out fully charged state volume test later, the volume of lithium ion battery is denoted as V1；It again will with the constant current of 1C
Lithium ion battery charges certain time to a certain overcharging state, and carries out overcharging state volume test, the volume of lithium ion battery
It is denoted as V2。
Cubical expansivity (%) the=[ of lithium ion battery;(V2-V1)/V1]× 100%.
Wherein, for LiNi1/3Co1/3Mn1/3O2System, overcharging state are 170% fully charged state (i.e. SOC)；For
LiNi0.5Co0.2Mn0.3O2System, overcharging state are then 150%SOC.
Overcharge test in require lithium ion battery to reach overcharging state after in 2 minutes the cubical expansivity of lithium ion battery reach
To 100%, battery safety device can be triggered at this time, opens current control safety valve gas is discharged to exterior space, as
Test is overcharged to pass through.
(2) D.C. resistance (DCR) test of lithium ion battery
At 25 DEG C, 4.2V is charged to lithium ion battery with the constant current of 1C, is further filled with 4.2V constant voltages
Electricity to electric current is less than 0.05C, and the 6min that then discharged respectively lithium ion battery with the discharge current of 1C is filled to lithium ion battery
Electricity condition is 90% fully charged state (i.e. 90%SOC), and discharge 30min to 50%SOC, and 48min is to 20%SOC for electric discharge, then distinguishes
With 4C discharge currents to lithium-ion electric tank discharge 30s, the D.C. resistance under lithium ion battery difference charged state is tested.
(3) the cycle performance test of lithium ion battery
At 60 DEG C, charge and discharge cycles test is carried out to lithium ion battery with the charge and discharge galvanic electricity of 1C.Test lithium-ion electric
Capacity retention ratio after the cycle of pond.
(4) the storage performance test of lithium ion battery
At 25 DEG C, lithium ion battery is first charged to by 4.2V with the constant current of 1C, further with 4.2V constant voltages
It charges to electric current and is less than 0.05C, then store lithium ion battery at 45 DEG C and 60 DEG C respectively, test lithium ion battery storage
Capacity retention ratio afterwards.
Table 1 provides the parameter and the performance test results of comparative example 1-5 and embodiment 1-7.
The parameter and the performance test results of table 1 comparative example 1-5 and embodiment 1-7
The comparison of comparative example 1 and comparative example 3, comparative example 4 and comparative example 5 is it is found that anti-overcharge addition in electrolyte from table 1
The addition of agent can make lithium ion battery have good gas generation property in overcharging state, be tested by overcharging, but its band
Chemical property deterioration when the lithium ion battery normal use come is also fairly obvious, after the storage 90 days of 45 DEG C of lithium ion battery
Capacity retention ratio declines rapidly.From the comparison of comparative example 3 and embodiment 1, comparative example 5 and embodiment 6 it is found that the addition of Quercetin
The lithium ion battery electrochemistry caused by the addition of anti-overcharge additive when lithium ion battery normal use can effectively be made up
The problem of energy severe exacerbation.And from embodiment 1-2 comparison it is found that with Quercetin addition increase, to lithium-ion electric
The improvement of pond chemical property is more apparent.
Fig. 1 shows the D.C. resistance of comparative example 1 and comparative example 2 under different charged states at 25 DEG C, Fig. 2 and Fig. 3 difference
Capacity retention ratio after capacity retention ratio and cycle is shown at 60 DEG C after the storage of comparative example 1 and comparative example 2.It can from Fig. 1-3
Go out, being added for independent Quercetin can improve lithium-ion electric while reducing the D.C. resistance of lithium ion battery in electrolyte
The storage performance and cycle performance in pond.
Fig. 4 shows that the D.C. resistance of comparative example 4-5 and embodiment 6 under different charged states at 25 DEG C, Fig. 5 and Fig. 6 divide
Capacity retention ratio after the storage of comparative example 4-5 and embodiment 6 and the capacity retention ratio after cycle at 60 DEG C are not shown.From Fig. 4-
In 6 and the data result of the capacity retention ratio in table 1 after the storage 90 days of 45 DEG C of lithium ion battery is combined to can be seen that Quercetin
Addition can effectively make up lithium ion battery battery when lithium ion battery normal use caused by the addition of anti-overcharge additive
The problem of chemical property severe exacerbation, while reducing the D.C. resistance of lithium ion battery.This is primarily due to anti-overcharge additive
Can be in positive polymerization film formation, and it is finer and close, larger at film resistance to form a film, electron conduction and ion conduction are poor, cause lithium from
Sub- battery performance deteriorates, and the addition of Quercetin can be formed a film with auxiliary positive, improves into membrane structure, and forming one kind has
Good space structure and electron conduction and the good elastomeric state structure of ion conduction, are ensureing that it is resistance to that lithium ion battery has had
The chemical property for making lithium ion battery also have while over-charging.
Claims (10)
1. a kind of lithium-ion battery electrolytes, including：
Lithium salts；And
Non-aqueous organic solvent；
It is characterized in that,
The electrolyte further includes anti-overcharge additive and auxiliary film for additive；
The structural formula of the anti-overcharge additive is as follows：
Wherein, the H on 1,2,3,4,5,6 is replaced by alkyl, naphthenic base, F or phenyl each independently；
The structural formula of the auxiliary film for additive is as follows：
Wherein, the H on 3,5,6,7,8,1 ', 2 ', 3 ', 4 ' and 5 ' positions is each independently by phenolic hydroxyl group, hydroxyl, alkyl, alcoxyl
Base, carboxyl, amino, aromatic radical or the above-mentioned functional group of halogen substitution are replaced.
2. lithium-ion battery electrolytes according to claim 1, which is characterized in that the anti-overcharge additive is selected from connection
One or more of benzene, cyclohexyl benzene, meta-terphenyl, phenyl-pentafluoride, tert-butyl benzene, tert-amyl benzene and 2- fluorine biphenyl.
3. lithium-ion battery electrolytes according to claim 1, which is characterized in that the anti-overcharge additive is in lithium ion
Mass percentage in battery electrolyte is 0.5%~8%.
4. lithium-ion battery electrolytes according to claim 1, which is characterized in that the auxiliary film for additive is quercitrin
Element, structural formula are as follows：
5. lithium-ion battery electrolytes according to claim 1, which is characterized in that the auxiliary film for additive lithium from
Mass percentage in sub- battery electrolyte is 0.002%~0.1%.
6. lithium-ion battery electrolytes according to claim 1, which is characterized in that the non-aqueous organic solvent is selected from carbonic acid
One or more of vinyl acetate, propene carbonate, dimethyl carbonate, diethyl carbonate and methyl ethyl carbonate.
7. lithium-ion battery electrolytes according to claim 1, which is characterized in that the lithium salts be selected from LiTFSI,
LiFSI、LiN(CxF2x+1SO2)(CyF2y+1SO2)、LiPF6、LiBF4、LiBOB、LiAsF6、LiCF3SO3And LiClO4In one
Kind is several, and wherein x, y are natural number.
8. lithium ion battery according to claim 1, which is characterized in that a concentration of 0.8mol/L~1.5mol/ of lithium salts
L。
9. a kind of lithium ion battery, including：
Anode pole piece, including plus plate current-collecting body and be set on plus plate current-collecting body and include positive electrode active materials, conductive agent and
The positive diaphragm of binder；
Cathode pole piece, including negative current collector and be set on negative current collector and include negative electrode active material, conductive agent and
The cathode membrane of binder；
Isolation film is interval between anode pole piece and cathode pole piece；And
Electrolyte；
It is characterized in that, the electrolyte is the lithium-ion battery electrolytes according to any one of claim 1-8.
10. lithium ion battery according to claim 9, which is characterized in that
The positive electrode active materials are selected from LiCoO2、LiMn2O4、LiNi1/3Co1/3Mn1/3And Li (CoxNiyMn1-x-y)O2In
It is one or more of, wherein 0.3≤x≤0.8,0.1≤y≤0.4,0.6≤x+y≤0.9；
The negative electrode active material is selected from graphite and/or silicon；
The isolation film is selected from one or more of polyolefin film and polyolefin/ceramic coating composite membrane.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1925206A (en) * | 2006-09-20 | 2007-03-07 | 广州市天赐高新材料科技有限公司 | Dynamic electrolyte for lithium ion battery |
| CN101017913A (en) * | 2006-02-08 | 2007-08-15 | 深圳市比克电池有限公司 | A lithium ion battery electrolyte |
| CN102263292A (en) * | 2011-06-24 | 2011-11-30 | 九江天赐高新材料有限公司 | Non-aqueous electrolytic solution used for lithium secondary batteries |
| CN103887560A (en) * | 2012-12-21 | 2014-06-25 | 上海比亚迪有限公司 | Non-aqueous electrolyte and lithium ion battery containing the non-aqueous electrolyte |
| CN104218258A (en) * | 2014-09-17 | 2014-12-17 | 宜春金晖新能源材料有限公司 | Over-charging prevention flame-retardant battery electrolyte |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101017913A (en) * | 2006-02-08 | 2007-08-15 | 深圳市比克电池有限公司 | A lithium ion battery electrolyte |
| CN1925206A (en) * | 2006-09-20 | 2007-03-07 | 广州市天赐高新材料科技有限公司 | Dynamic electrolyte for lithium ion battery |
| CN102263292A (en) * | 2011-06-24 | 2011-11-30 | 九江天赐高新材料有限公司 | Non-aqueous electrolytic solution used for lithium secondary batteries |
| CN103887560A (en) * | 2012-12-21 | 2014-06-25 | 上海比亚迪有限公司 | Non-aqueous electrolyte and lithium ion battery containing the non-aqueous electrolyte |
| CN104218258A (en) * | 2014-09-17 | 2014-12-17 | 宜春金晖新能源材料有限公司 | Over-charging prevention flame-retardant battery electrolyte |
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