CN106531971A - Intelligent high-safety lithium-on battery with polymer skeleton - Google Patents
Intelligent high-safety lithium-on battery with polymer skeleton Download PDFInfo
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- CN106531971A CN106531971A CN201611141317.2A CN201611141317A CN106531971A CN 106531971 A CN106531971 A CN 106531971A CN 201611141317 A CN201611141317 A CN 201611141317A CN 106531971 A CN106531971 A CN 106531971A
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- 229920000642 polymer Polymers 0.000 title claims abstract description 90
- 239000007788 liquid Substances 0.000 claims abstract description 22
- 239000003792 electrolyte Substances 0.000 claims abstract description 18
- 239000011244 liquid electrolyte Substances 0.000 claims abstract description 18
- 239000012528 membrane Substances 0.000 claims abstract description 7
- 239000002245 particle Substances 0.000 claims abstract description 7
- 229910001416 lithium ion Inorganic materials 0.000 claims description 56
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 41
- 239000008187 granular material Substances 0.000 claims description 38
- 229910052744 lithium Inorganic materials 0.000 claims description 30
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 29
- 230000004888 barrier function Effects 0.000 claims description 22
- -1 dimethylammonium isobutene Chemical compound 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 17
- 239000000126 substance Substances 0.000 claims description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 9
- 238000003860 storage Methods 0.000 claims description 9
- 239000013543 active substance Substances 0.000 claims description 8
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 claims description 8
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims description 7
- 150000002148 esters Chemical class 0.000 claims description 7
- 229920003063 hydroxymethyl cellulose Polymers 0.000 claims description 7
- 229940031574 hydroxymethyl cellulose Drugs 0.000 claims description 7
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 6
- 239000010941 cobalt Substances 0.000 claims description 6
- 229910017052 cobalt Inorganic materials 0.000 claims description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 6
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 claims description 5
- 229910021389 graphene Inorganic materials 0.000 claims description 5
- PSBDWGZCVUAZQS-UHFFFAOYSA-N (dimethylsulfonio)acetate Chemical compound C[S+](C)CC([O-])=O PSBDWGZCVUAZQS-UHFFFAOYSA-N 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- 239000004743 Polypropylene Substances 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 229910002804 graphite Inorganic materials 0.000 claims description 4
- 239000010439 graphite Substances 0.000 claims description 4
- 150000002500 ions Chemical class 0.000 claims description 4
- 229920001155 polypropylene Polymers 0.000 claims description 4
- 229940117986 sulfobetaine Drugs 0.000 claims description 4
- 229910052493 LiFePO4 Inorganic materials 0.000 claims description 3
- 239000004698 Polyethylene Substances 0.000 claims description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- 229920000573 polyethylene Polymers 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 claims description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 2
- 239000002033 PVDF binder Substances 0.000 claims description 2
- 229910003481 amorphous carbon Inorganic materials 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 239000006258 conductive agent Substances 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 239000011572 manganese Substances 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims 2
- QHGNHLZPVBIIPX-UHFFFAOYSA-N tin(II) oxide Inorganic materials [Sn]=O QHGNHLZPVBIIPX-UHFFFAOYSA-N 0.000 claims 2
- 150000001408 amides Chemical class 0.000 claims 1
- 238000005868 electrolysis reaction Methods 0.000 claims 1
- 239000004744 fabric Substances 0.000 claims 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims 1
- 239000004408 titanium dioxide Substances 0.000 claims 1
- 230000001351 cycling effect Effects 0.000 abstract 1
- 239000005518 polymer electrolyte Substances 0.000 abstract 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 10
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 5
- 241000233803 Nypa Species 0.000 description 5
- 235000005305 Nypa fruticans Nutrition 0.000 description 5
- 239000012530 fluid Substances 0.000 description 5
- 239000007924 injection Substances 0.000 description 5
- 238000002347 injection Methods 0.000 description 5
- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 0.000 description 5
- 230000036961 partial effect Effects 0.000 description 5
- 238000003466 welding Methods 0.000 description 5
- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 4
- 239000010452 phosphate Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 239000008202 granule composition Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229920006266 Vinyl film Polymers 0.000 description 1
- CHBCHAGCVIMDKI-UHFFFAOYSA-N [F].C=C Chemical group [F].C=C CHBCHAGCVIMDKI-UHFFFAOYSA-N 0.000 description 1
- 238000001467 acupuncture Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/137—Electrodes based on electro-active polymers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—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
-
- 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)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Secondary Cells (AREA)
Abstract
The invention discloses an intelligent high-safety lithium-on battery with a polymer skeleton. The intelligent high-safety lithium-on battery comprises a positive electrode, a negative electrode, a membrane and an electrolyte, wherein the positive electrode, the negative electrode and the membrane all contain positive-temperature temperature-sensitive polymer particles; the lithium-on battery can be reversibly converted between a ''liquid lithium-on battery'' and a ''polymer lithium-on battery'' within different temperature ranges; the electrolyte in the ''liquid lithium-on battery'' exists in a form of a liquid electrolyte; and the electrolyte in the ''polymer lithium-on battery'' exists in a form of a polymer electrolyte. The lithium-on battery disclosed by the invention is quickly converted into the ''polymer lithium-on battery'' when the temperature suddenly rises, and does not contain the liquid electrolyte, so that an unstable solid-liquid interface can be removed and the interface stability of the battery can be effectively improved; and by adopting the polymer skeleton, the positive electrode, the negative electrode and the membrane of the battery are tightly connected, and the stability of the battery structure can be improved, so that the lithium-on battery can show good cycling stability and excellent electrochemical properties at different temperatures and is suitable for various complicated environments.
Description
Technical field
The invention belongs to technical field of lithium ion, is related to a kind of intelligent polymer skeleton highly secure lithium ion battery.
Background technology
With the fast development of new-energy automobile industry, the development of power-type lithium ion battery also receives great market
Driving force.Requirement of the people to power lithium-ion battery is also towards high-energy-density, high power density, high safety performance, longevity
The aspects such as life, extensive environmental suitability develop.At present, business-like power lithium-ion battery it is universal with graphite as negative pole, phosphorus
It is barrier film that sour ferrum lithium or cobalt acid lithium are positive pole, polyolefin porous membrane, and electrolyte is present in liquid form.With high-energy-density
Electrode material is introduced, such as silicon systems negative pole, stannum system negative pole, Graphene negative pole, tertiary cathode etc., the solid-liquid interface stability of battery,
The performance such as service life and safety significantly declines, and has had a strong impact on application and development of the lithium ion battery in automobile industry.
Therefore, the solid-liquid interface and safety problem for how solving lithium ion battery becomes research emphasis.
Polymer Li-ion battery is grown up on the basis of conventional liquid lithium ion battery with more Gao An at present
The battery of full performance.Polymer Li-ion battery replaces liquid electrolyte using polymer dielectric, can be prevented effectively from battery
Leakage problem simultaneously avoids the presence of solid liquid interface.Simultaneously the shell of existing polymer battery adopts light plastic flexible package, can be with
Battery weight is reduced, battery energy density is lifted.A kind of polymer electrolytic of auto polymerization is disclosed in patent CN101685876B
The preparation method of matter, adds polymerization reaction monomer and initiator in liquid electrolyte, and trigger monomer occurs at a certain temperature
Liquid electrolyte is converted into polymer dielectric by Raolical polymerizable.Disclose a kind of poly- in patent CN102610830B
Compound lithium ion battery, using porosity ion conductive polymer glue layer, both positive and negative polarity collector with many permeability holes improve every
Bonding force between film and both positive and negative polarity, removes liquid electrolyte, effectively lifts stability and the safety of battery structure.
Above-mentioned polymer Li-ion battery, after polymerization condition is reached, lithium ion battery is completed to polymer Li-ion
The process of cells convert, and this conversion is irreversible.Polymer Li-ion battery has excellent at aspects such as interface, safety
Gesture, but polymer is in the excessive aggregation in interface, can also reduce electronics and pass to speed with ion, it is suppressed that the multiplying power of battery is special
Property, increase the quantity of heat production of battery.The scope of application of polymer Li-ion battery is largely limited, is especially led in power
The application in domain.
The content of the invention
It is an object of the invention to provide a kind of highly secure lithium ion battery, which overcomes the solid-liquid of existing lithium ion battery
Interface and safety problem, and the multiplying power property of battery is not affected, in complicated working environment, can also represent good circulation steady
Qualitative and superior chemical property, it is adaptable to dynamic field.
To reach above-mentioned purpose, the invention provides a kind of intelligent polymer skeleton highly secure lithium ion battery, which includes
Positive pole, negative pole, barrier film and electrolyte, described positive pole, negative pole, barrier film contain positive warm type temperature sensitive polymer granule, wherein,
Under different temperature ranges, the lithium ion battery can be between " liquid lithium ionic cell " and " polymer Li-ion battery " mutually
Conversion, in described " liquid lithium ionic cell ", electrolyte is present with liquid electrolyte form；Described " polymer Li-ion electricity
In pond ", electrolyte is present with polymer dielectric form.
Described positive warm type temperature sensitive polymer granule is selected in polysulfonate base dimethylammonium isobutene. ester, polysulfonate base trimethylammonium second
In ester, NIPA or polymethylacrylic acid N, N- dimethylaminoethyl granule any one or a few
Mixture.
The weight average molecular weight of described positive warm type temperature sensitive polymer granule is 50000～1000000, and particle size is 0.1
～20um.
<Within the temperature range of 60 DEG C, the polymer molecular chain in described positive warm type temperature sensitive polymer granule is in reunion
Shape, does not absorb liquid electrolyte.
Within the temperature range of 60～120 DEG C, the polymer molecular chain in described positive warm type temperature sensitive polymer granule
Entanglement form is launched to become long-chain shape by shape of reuniting, and can absorb liquid electrolyte.
Described positive pole by with the storage active substance of lithium ability, positive warm type temperature sensitive polymer granule, Kynoar, lead
Electric agent is according to 85～100：0.5～5：3～5：1～5 weight ratio composition, wherein, the active substance with storage lithium ability is cobalt
Sour lithium, LiMn2O4, LiFePO4, nickel-cobalt-manganese ternary, manganese systems binary, cobalt system binary or nickel system binary, or for above-mentioned substance
Complex.
Described negative pole by with the storage active substance of lithium ability, positive warm type temperature sensitive polymer granule, hydroxymethyl cellulose,
Butadiene-styrene rubber, conductive agent are according to 85～100：0.5～5：1.5～2.5：3～5：1～5 weight is than composition, wherein storage lithium ability
Active substance be Delanium, native graphite, amorphous carbon, Graphene, silicon, silicon monoxide, silicon dioxide, stannum, one oxidation
Stannum or tin ash, or for the complex of above-mentioned substance.
Described barrier film is by apertured polymeric film and positive warm type temperature sensitive polymer SiC p surface plating or the positive temperature of internal doping
Type temperature sensitive polymer granule is constituted, wherein, apertured polymeric film is porous polyethylene membrane, porous polypropylene film, porous gather inclined fluorine
Vinyl film, non-woven fabrics, or for the complex of above-mentioned substance.
The intelligent polymer skeleton highly secure lithium ion battery of the present invention, during normal use, in liquid electrolyte
Ion can be little in inside battery fast transferring, the internal resistance of battery, with excellent big multiplying power property and cyclical stability；When
Ambient temperature raised suddenly, or battery when there is the situations such as punctures, short circuit, and the temperature of battery rapidly can rise, and temperature is higher than 60
After DEG C, the battery is changed into rapidly polymer Li-ion battery.Now the battery does not contain liquid electrolyte, it is to avoid electrolyte
It is heated and volatilizees and decompose, effectively eliminates unstable solid-liquid interface.Polymer backbone makes anode, negative pole, barrier film shape simultaneously
Into close-connected entirety, battery structure stability and safety are lifted.When ambient temperature recovers normal, or puncture, short circuit
After disappearing etc. situation, battery temperature is gradually decrease to less than 60 DEG C, and battery is changed into " liquid by " polymer Li-ion battery " again
Lithium ion battery ", continues the stable performance storage advantage such as lithium performance and high rate charge-discharge.
In a word, the intelligent polymer skeleton highly secure lithium ion battery that the present invention is provided can represent good at different temperatures
Good cyclical stability and superior chemical property, are a kind of high safety lithium ion power electricity suitable for various complicated
Pond.
Description of the drawings
Fig. 1 is a kind of intelligent polymer skeleton highly secure lithium ion battery of the invention structural representation at a lower temperature
Figure.
Fig. 2 is a kind of intelligent polymer skeleton highly secure lithium ion battery of the invention structural representation at relatively high temperatures
Figure.
Specific embodiment
Below in conjunction with accompanying drawing, by specific embodiment, the invention will be further described, and these embodiments are merely to illustrate
The present invention, is not limiting the scope of the invention.
As shown in figure 1, for the present invention a kind of intelligent polymer skeleton highly secure lithium ion battery in lower temperature (e.g.,
60 DEG C of ＜) working condition, which includes positive pole 1, negative pole 2, barrier film 3 and electrolyte, and described positive pole 1, negative pole 2, barrier film 3 contain
There is positive warm type temperature sensitive polymer granule 4, the polymer molecular chain in the positive warm type temperature sensitive polymer granule is in reunion shape, is not absorbed
Liquid electrolyte, now, lithium ion battery is rendered as liquid lithium ionic cell, and electrolyte is present with liquid electrolyte form.
As shown in Fig. 2 for the present invention a kind of intelligent polymer skeleton highly secure lithium ion battery in higher temperature (e.g.,
60～120 DEG C) working condition, which includes positive pole 1, negative pole 2, barrier film 3 and electrolyte, described positive pole 1, negative pole 2, barrier film 3
In the positive warm type temperature sensitive polymer granule that contains be converted to polymer backbone 5, the polymer molecule in positive warm type temperature sensitive polymer
The entanglement form of chain is launched to become long-chain shape by shape of reuniting, and can absorb liquid electrolyte, and now the battery does not contain liquid electrolyte,
The battery changes into rapidly polymer Li-ion battery, and electrolyte is present with polymer dielectric form.
Embodiment 1
The positive warm type temperature sensitive polymer granule of this example is polysulfonate base dimethylammonium isobutene. ester granule, and weight average molecular weight is
100000, particle size is 0.5um.Positive pole by nickel-cobalt-manganese ternary, polysulfonate base dimethylammonium isobutene. ester granule, Kynoar,
Super P are according to 92：1：3.5：3.5 percentage by weight composition.Negative pole is by Delanium, polysulfonate base dimethylammonium isobutene. ester
Grain, hydroxymethyl cellulose, butadiene-styrene rubber, super P are according to 92.5：1：2：3：1.5 percentage by weights are constituted.Barrier film is gathered by porous
The thick polysulfonate base dimethylammonium isobutene. ester granule composition of propylene film surface-coated 2um.Electrolyte is by EC (ethylene carbonate)：EMC
(Ethyl methyl carbonate)：DEM (diethyl carbonate) is according to 1：1：1.2 ratios, and dissolve the lithium hexafluoro phosphate composition of 1mol/L.Will just
Pole piece, barrier film, negative plate are stacked successively and make battery core using laminated structure, and after being respectively welded positive and negative electrode lug, then Jing enters
After shell, laser welding, fluid injection, chemical conversion and partial volume operation, described intelligent polymer skeleton highly secure lithium ion battery is obtained.
Embodiment 2
The positive warm type temperature sensitive polymer granule of this example is poly- sulfobetaine granule, and weight average molecular weight is
100000, particle size is 0.4um.Positive pole by nickel-cobalt-manganese ternary, poly- sulfobetaine granule, Kynoar,
Super P are according to 93：1.5：3：2.5 percentage by weight composition.Negative pole is by Graphene, silicon monoxide, polysulfonate base trimethylammonium second
Lactone granule, hydroxymethyl cellulose, butadiene-styrene rubber, super P are according to 80：10：2：2：3：3 percentage by weight composition.Barrier film
It is made up of the thick poly- sulfobetaine granule of porous polyethylene membrane surface-coated 1.5um.Electrolyte is by EC (ethylene carbonates
Ester)：EMC (Ethyl methyl carbonate)：DEM (diethyl carbonate) is according to 1：1.5：1 ratio, and dissolve the lithium hexafluoro phosphate of 1.2mol/L
Composition.Positive plate, barrier film, negative plate are stacked successively and battery core is made using laminated structure, be respectively welded positive and negative electrode lug
Afterwards, then Jing after entering shell, laser welding, fluid injection, chemical conversion and partial volume operation, obtain described intelligent polymer skeleton high safety lithium from
Sub- battery.
Embodiment 3
The positive warm type temperature sensitive polymer granule of this example is NIPA granule, and weight average molecular weight is
50000, particle size is 10um.Positive pole is by LiFePO4, NIPA granule, Kynoar, super
P is according to 93：1.5：3：2.5 percentage by weight composition.Negative pole is by Graphene, silicon monoxide, NIPA
Granule, hydroxymethyl cellulose, butadiene-styrene rubber, super P are according to 85：5：2：2：3：3 percentage by weight composition.Barrier film is by porous
The thick NIPA granule composition of polyvinylidene fluoride film surface-coated 1um.Electrolyte is by EC (ethylene carbonates
Ester)：EMC (Ethyl methyl carbonate)：DEM (diethyl carbonate) is according to 1：1：1 ratio, and dissolve the lithium hexafluoro phosphate group of 1mol/L
Into.Positive plate, barrier film, negative plate are stacked successively and battery core is made using laminated structure, be respectively welded positive and negative electrode lug
Afterwards, then Jing after entering shell, laser welding, fluid injection, chemical conversion and partial volume operation, obtain described intelligent polymer skeleton high safety lithium from
Sub- battery.
Embodiment 4
The positive warm type temperature sensitive polymer granule of this example be polymethylacrylic acid N, N- dimethylaminoethyl granules, Weight-average molecular
Measure as 50000, particle size is 10um.Positive pole is by cobalt acid lithium, polymethylacrylic acid N, N- dimethylaminoethyl granules, poly- inclined fluorine
Ethylene, super P are according to 93.5：1：3：2.5 percentage by weight composition.Negative pole is by native graphite, polymethylacrylic acid N, N-
Dimethylaminoethyl granule, hydroxymethyl cellulose, butadiene-styrene rubber, super P are according to 90：2：2：3：3 percentage by weight composition.
Barrier film coats the thick polymethylacrylic acid N of 1um, N- dimethylaminoethyls granule composition by porous polypropylene nonwoven surface.Electricity
Solution liquid is by EC (ethylene carbonate)：EMC (Ethyl methyl carbonate)：DEM (diethyl carbonate) is according to 1：1.2：1 ratio, and dissolve
The lithium hexafluoro phosphate composition of 1mol/L.Positive plate, barrier film, negative plate are stacked successively and battery core are made using laminated structure,
After being respectively welded positive and negative electrode lug, then Jing after entering shell, laser welding, fluid injection, chemical conversion and partial volume operation, described intelligence is obtained
Polymer backbone highly secure lithium ion battery.
Comparative example 1
This example positive pole is by nickel-cobalt-manganese ternary, Kynoar, super P according to 93：3.5：3.5 percentage by weight group
Into.Negative pole is by Delanium, hydroxymethyl cellulose, butadiene-styrene rubber, super P according to 93.5：2：3：1.5 percentage by weight group
Into.Barrier film is porous polypropylene film, and electrolyte is by EC (ethylene carbonate)：EMC (Ethyl methyl carbonate)：DEM (diethyl carbonate)
According to 1：1：1.2 ratios, and dissolve the lithium hexafluoro phosphate composition of 1mol/L.Positive plate, barrier film, negative plate are stacked successively and adopted
Battery core is made with laminated structure, after being respectively welded positive and negative electrode lug, then Jing enters shell, laser welding, fluid injection, chemical conversion and partial volume
After operation, lithium ion battery is obtained.
By 1～4 intelligent polymer skeleton highly secure lithium ion battery of embodiment and 1 lithium ion battery of comparative example by following
Method tests temperature varied cyclical performance and security performance, as a result as shown in table 1.
Temperature varied cyclical performance：Battery circulate successively under 25 DEG C/60 DEG C/80 DEG C/25 DEG C of temperature schedule, respectively 200 times/
50 times/50 times/200 times, concrete test parameter is as follows：By battery 1C constant-current charges to upper limit blanking voltage, then constant-voltage charge,
Cut-off current is 0.05C；Subsequently by battery 1C multiplying powers constant-current discharge to 2.5V, the initial discharge capacity C of battery is obtained0, then
Charge and discharge cycles are carried out to battery according to above-mentioned discharge and recharge system, the capacitance for obtaining battery is Cd, according to L=Cd/C0×
100% method calculates the discharge capacitance of battery after circulation.
Safety of acupuncture energy：By battery in the way of CC-CV after the fully charged blanking voltage to the upper limit, with Φ 3mm～Φ 8mm's
High temperature resistant draw point, with the speed of 10mm/s～40mm/s, runs through from the direction perpendicular to accumulator plate, and draw point rests on battery
Middle 1h.
Short circuit safety energy：By battery in the way of CC-CV after the fully charged blanking voltage to the upper limit, using internal resistance<5mΩ
Outside line short circuit 10min.
The result of security performance test is defined, " not on fire blast of not smoldering " is " outstanding ", " smolder, have Mars, it is not quick-fried
It is fried " for " general ", " blast on fire " is " disappointing ".
Table 1：The battery performance test result of embodiment 1～4 and comparative example
From table 1, the intelligent polymer skeleton highly secure lithium ion battery of embodiment 1～4 is in the temperature higher than 60 DEG C
Under, still with more than 88% capability retention.When temperature is recovered to 25 DEG C, capability retention rises to 93.5%～
95.1%.
In sum, the invention provides a kind of intelligent polymer skeleton highly secure lithium ion battery, can be according to difference
Ambient temperature realize flexible reversible transformation between " liquid lithium ionic cell " and " polymer Li-ion battery ".Higher
At a temperature of, " polymer Li-ion battery " is transformed into by " liquid lithium ionic cell "；At a lower temperature by " polymer Li-ion
Battery " becomes " liquid lithium ionic cell ".And, the intelligent polymer skeleton highly secure lithium ion battery that the present invention is provided is not
It is synthermal lower equal to represent good cyclical stability and superior chemical property.
Although present disclosure has been made to be discussed in detail by above preferred embodiment, but it should be appreciated that above-mentioned
Description is not considered as limitation of the present invention.After those skilled in the art have read the above, for the present invention's
Various modifications and substitutions all will be apparent.Therefore, protection scope of the present invention should be limited to the appended claims.
Claims (8)
1. a kind of intelligent polymer skeleton highly secure lithium ion battery, which includes positive pole (1), negative pole (2), barrier film (3) and electrolysis
Liquid, it is characterised in that described positive pole (1), negative pole (2), barrier film (3) contain positive warm type temperature sensitive polymer granule (4), its
In, under different temperature ranges, the lithium ion battery can " liquid lithium ionic cell " and " polymer Li-ion battery " it
Between mutually change, in described " liquid lithium ionic cell " electrolyte with liquid electrolyte form exist；Described " polymer lithium
In ion battery ", electrolyte is present with polymer dielectric form.
2. intelligent polymer skeleton highly secure lithium ion battery as claimed in claim 1, it is characterised in that described positive warm type
Temperature sensitive polymer granule (4) selects polysulfonate base dimethylammonium isobutene. ester, poly- sulfobetaine, poly- (N- isopropyl propylene
Amide) or polymethylacrylic acid N, N- dimethylaminoethyl granule in any one or a few mixture.
3. intelligent polymer skeleton highly secure lithium ion battery as claimed in claim 1, it is characterised in that described positive warm type
The weight average molecular weight of temperature sensitive polymer granule (4) is 50000～1000000, and particle size is 0.1～20um.
4. intelligent polymer skeleton highly secure lithium ion battery as claimed in claim 1, it is characterised in that<60 DEG C of temperature
In the range of degree, the polymer molecular chain in described positive warm type temperature sensitive polymer granule (4) is in reunion shape, does not absorb liquid electrolyte
Liquid.
5. intelligent polymer skeleton highly secure lithium ion battery as claimed in claim 1, it is characterised in that at 60～120 DEG C
Within the temperature range of, the entanglement form of the polymer molecular chain in described positive warm type temperature sensitive polymer granule (4) is by shape of reuniting
Expansion becomes long-chain shape, can absorb liquid electrolyte.
6. intelligent polymer skeleton highly secure lithium ion battery as claimed in claim 1, it is characterised in that described positive pole
(1) by with the storage active substance of lithium ability, positive warm type temperature sensitive polymer granule (4), Kynoar, conductive agent according to 85～
100：0.5～5：3～5：1～5 weight than composition, wherein, the active substance with storage lithium ability be cobalt acid lithium, LiMn2O4,
LiFePO4, nickel-cobalt-manganese ternary, manganese systems binary, cobalt system binary or nickel system binary, or for the complex of above-mentioned substance.
7. intelligent polymer skeleton highly secure lithium ion battery as claimed in claim 1, it is characterised in that described negative pole
(2) by with the storage active substance of lithium ability, positive warm type temperature sensitive polymer granule (4), hydroxymethyl cellulose, butadiene-styrene rubber, lead
Electric agent is according to 85～100：0.5～5：1.5～2.5：3～5：1～5 weight is than composition, wherein the active substance of storage lithium ability
For Delanium, native graphite, amorphous carbon, Graphene, silicon, silicon monoxide, silicon dioxide, stannum, tin monoxide or titanium dioxide
Stannum, or for the complex of above-mentioned substance.
8. intelligent polymer skeleton highly secure lithium ion battery as claimed in claim 1, it is characterised in that described barrier film
(3) by apertured polymeric film and positive warm type temperature sensitive polymer granule (4) surface-coated or the positive warm type temperature sensitive polymer of internal doping
Granule (4) is constituted, wherein, apertured polymeric film is porous polyethylene membrane, porous polypropylene film, porous polyvinylidene fluoride film, nothing
Cloth is spun, or for the complex of above-mentioned substance.
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| CN108695489A (en) * | 2017-03-30 | 2018-10-23 | 丰田自动车株式会社 | The manufacturing method of electrode |
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| CN110858521A (en) * | 2018-08-26 | 2020-03-03 | 天津大学 | Reversible overheat protection aqueous electrolyte based on poly (isopropyl acrylamide) -methacrylic acid and preparation method and application thereof |
| CN110938170A (en) * | 2018-09-25 | 2020-03-31 | 天津大学 | Reversible overheat protection aqueous electrolyte based on methyl fiber grafted isopropyl acrylamide and preparation method and application thereof |
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| JP2023508037A (en) * | 2020-01-20 | 2023-02-28 | エルジー エナジー ソリューション リミテッド | SOLID-LIQUID HYBRID ELECTROLYTE MEMBRANE AND METHOD FOR MANUFACTURING SAME |
| JP7500730B2 (en) | 2020-01-20 | 2024-06-17 | エルジー エナジー ソリューション リミテッド | Solid-liquid hybrid electrolyte membrane and its manufacturing method |
| CN113690439A (en) * | 2021-07-27 | 2021-11-23 | 惠州锂威新能源科技有限公司 | Temperature-sensitive slurry, preparation method thereof, pole piece and secondary battery |
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Application publication date: 20170322 |