CN106374112A - Lithium battery and positive electrode coating copolymer thereof - Google Patents
Lithium battery and positive electrode coating copolymer thereof Download PDFInfo
- Publication number
- CN106374112A CN106374112A CN201510464195.XA CN201510464195A CN106374112A CN 106374112 A CN106374112 A CN 106374112A CN 201510464195 A CN201510464195 A CN 201510464195A CN 106374112 A CN106374112 A CN 106374112A
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- CN
- China
- Prior art keywords
- lithium battery
- positive
- lithium
- pole coating
- coating
- Prior art date
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 55
- 238000000576 coating method Methods 0.000 title claims abstract description 41
- 239000011248 coating agent Substances 0.000 title claims abstract description 39
- 229920001577 copolymer Polymers 0.000 title claims abstract description 28
- 239000000463 material Substances 0.000 claims abstract description 47
- 239000012528 membrane Substances 0.000 claims description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 14
- 230000004308 accommodation Effects 0.000 claims description 14
- 239000003792 electrolyte Substances 0.000 claims description 12
- 239000003575 carbonaceous material Substances 0.000 claims description 7
- 229910002804 graphite Inorganic materials 0.000 claims description 7
- 239000010439 graphite Substances 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical group [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 5
- -1 hexafluorophosphoric acid Lithium Chemical compound 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 5
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 4
- 239000000853 adhesive Substances 0.000 claims description 4
- 230000001070 adhesive effect Effects 0.000 claims description 4
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- 150000001335 aliphatic alkanes Chemical group 0.000 claims description 3
- 239000011889 copper foil Substances 0.000 claims description 3
- 239000011883 electrode binding agent Substances 0.000 claims description 3
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims description 3
- 239000000178 monomer Substances 0.000 claims description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-methyl-pyrrolidinone Natural products CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- FBDMTTNVIIVBKI-UHFFFAOYSA-N [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] Chemical compound [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] FBDMTTNVIIVBKI-UHFFFAOYSA-N 0.000 claims description 2
- JKJWYKGYGWOAHT-UHFFFAOYSA-N bis(prop-2-enyl) carbonate Chemical compound C=CCOC(=O)OCC=C JKJWYKGYGWOAHT-UHFFFAOYSA-N 0.000 claims description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 2
- OCKPCBLVNKHBMX-UHFFFAOYSA-N butylbenzene Chemical compound CCCCC1=CC=CC=C1 OCKPCBLVNKHBMX-UHFFFAOYSA-N 0.000 claims 2
- 239000003292 glue Substances 0.000 claims 1
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 claims 1
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 claims 1
- 230000008018 melting Effects 0.000 abstract description 4
- 238000002844 melting Methods 0.000 abstract description 4
- 239000000758 substrate Substances 0.000 abstract description 2
- 238000000034 method Methods 0.000 description 5
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 239000011149 active material Substances 0.000 description 4
- 230000004888 barrier function Effects 0.000 description 4
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 4
- 230000001771 impaired effect Effects 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 238000012360 testing method Methods 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- PFYQFCKUASLJLL-UHFFFAOYSA-N [Co].[Ni].[Li] Chemical compound [Co].[Ni].[Li] PFYQFCKUASLJLL-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000005030 aluminium foil Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical class [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 2
- 239000000571 coke Substances 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000010422 painting Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000004804 winding Methods 0.000 description 2
- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 229910052493 LiFePO4 Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- QELJHCBNGDEXLD-UHFFFAOYSA-N nickel zinc Chemical compound [Ni].[Zn] QELJHCBNGDEXLD-UHFFFAOYSA-N 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000011076 safety test Methods 0.000 description 1
- 239000010409 thin film 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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/665—Composites
- H01M4/667—Composites in the form of layers, e.g. coatings
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/50—Current conducting connections for cells or batteries
- H01M50/572—Means for preventing undesired use or discharge
- H01M50/574—Devices or arrangements for the interruption of current
- H01M50/581—Devices or arrangements for the interruption of current in response to temperature
-
- 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
Abstract
The invention relates to a lithium battery and a copolymer of a positive electrode coating thereof, wherein the positive electrode coating containing a butadiene-styrene-alkyl methacrylate copolymer is arranged on at least one surface of a positive electrode substrate, and the copolymer is a material capable of providing regional protection, so that when the lithium battery is damaged by foreign body puncture, external force impact and the like, the resistance is increased to form an open circuit due to the accelerated melting and thermal expansion of the structure in the range of a damaged region, and the undamaged region can continuously provide the charge and discharge capacity.
Description
Technical field
The present invention is the copolymer with regard to a kind of lithium battery and its positive pole coating, and espespecially one kind is in lithium battery
When being had by external impacts part-structure impaired, can avoid overheated on fire, also can maintain certain ability to work
The tool lithium battery of the safety and its copolymer of positive pole coating.
Background technology
Lithium battery is a kind of device that can convert chemical energy into electric energy, and it can be reused by charging,
And running voltage is high, energy density is big, weight compared to, compared with the batteries such as ni-mh, nickel zinc, NI-G, having
Amount is light, life-span length and the feature of environmental protection good the advantages of, be widely used at present in various electronic products.
Lithium battery usually contains positive electrode, isolating membrane, negative material and electrolyte；Wherein,
Positive electrode is generally with LiMn2O4 (limn2o4), LiFePO4 (lifepo4), nickel cobalt lithium (linicoo2) three
Planting is main material, and it adds conductive agent, resin binder in above-mentioned three kinds of positive active materials, and
It is coated on aluminum substrate, be distributed in thin thin layer.Negative material is then mainly based on material with carbon element, can enter one again
Step is divided into graphite system and coke system, and the gravimetric energy density of graphite system therein is higher, and the knot of material itself
Structure has systematicness, and the therefore design of the use to electronic product and charger relatively has advantage；And coke system
Negative material is very high in the irreversible capacitance of first time discharge and recharge reaction, but this material can be in higher charge and discharge
Make discharge and recharge under electric speed (c-rate), add that the discharge curve of this material is more oblique, be conducive to using voltage
The consumption of monitoring battery capacity.
Is then isolation diaphragm between positive and negative pole material, and it is a microporosity and porous thin film,
Material is typically based on pp, pe, and its function is to isolate positive and negative pole material, prevents short circuit generation, but its
Ion can be made to pass through.As for electrolyte, its major function is conducting lithium ions, and is so that main electrolyte is become
Point lithium salts dissolving, electrolyte must have a high-dielectric constant, and has good with lithium ion compatibility molten
Agent, does not hinder the low viscous organic solution of ion movement to be advisable, and the work in lithium-ions battery
It is necessary to be in liquid condition in temperature range, there is the characteristic that freezing point is low and boiling point is high.
At present defect in application for the lithium battery is to be short of safety, for example when battery by improper heating,
Overcharge, positive and negative pole material contacts with each other when leading to short circuit, all probably due to excessive temperature raises, and have
The burn even possibility of blast.In general, this situation is commonly done in battery and dropping, strongly being touched
When hitting or pierced through with external force by sharp objects.
In order to lift the safety of lithium battery, known techniques, when lithium battery temperature raises, reduce lithium electricity
The overall electric conductivity in pond.In this prior art method, it is in one of anode plate and negative plates or two
One layer of hot barrier layer is covered on polar board surface.Comprise to improve the inorganic material of hardness due in this hot barrier layer
Outward, when being additionally included in the rising of lithium battery temperature, the nm level material of hot start can be started, therefore work as lithium battery
When temperature raises, hot start Nanometer material produces cross-linking reaction and forms macromolecule, and then hinders the expansion of lithium ion
Dissipate and move, cause electric conductivity to decline, whole lithium battery is lost the job ability.
Content of the invention
The main object of the present invention, is the copolymer providing a kind of lithium battery and its positive pole coating, its
Have in positive plate and comprise butadiene-styrene-methacrylate copolymer
The positive pole coating of (butadiene-styrene-alkyl methacrylate copolymer), it can make lithium
During the infringements such as battery is being punctured by foreign body, external force collision, can be because structure accelerates melting and be subject in affected area
Thermal expansion, and so that resistance is increased and form open circuit, retain the working condition in intact region simultaneously.
It is another object of the present invention to provide the copolymer of a kind of lithium battery and its positive pole coating, its
Lithium battery hot-spot can be avoided on fire, and the running voltage of lithium battery can be kept, and also sustainable charging
And electric discharge.
Therefore, present invention is disclosed the copolymer of a kind of lithium battery and its positive pole coating, its structure comprises:
One positive plate, it comprises a positive-pole base material and a positive pole coating, and this positive pole coating comprises butadiene-styrene
- methacrylate copolymer；One isolating membrane, its adjacent to this positive plate, and and this positive plate between
There is one first accommodation space；One negative plate, it is adjacent to this isolating membrane, and has and this isolating membrane between
One second accommodation space；And an electrolyte, it is arranged at this first accommodation space and this second accommodation space.
And the chemical structural formula of the monomer of the copolymer of positive pole coating then comprises (c6h6)x、(c8h8)yAnd (c4h5o2r)z,
Wherein x > 1, y > 1, z > 1, and r be carbon number > 1 alkane chain.
Brief description
Fig. 1: it is the structural representation of a preferred embodiment of the present invention；
Fig. 2: it is the voltage in puncture test and the temperature variation of a preferred embodiment of the present invention, in order to represent thorn
Before wearing, pierce through when and pierce through after temperature and voltage；And
Fig. 3: its be charge-discharge test figure in a preferred embodiment for the present invention, in order to represent impaired after lithium battery
Still it is provided that the characteristic persistently using.
[figure number is to as directed]
1 positive plate
11 positive-pole base materials
12 positive pole coatings
2 isolating membrane
3 negative plates
31 base material of cathode
32 negative pole coatings
41 first accommodation spaces
42 second accommodation spaces
Specific embodiment
In order that the architectural feature of the present invention and the effect reached have a better understanding and awareness,
Spy's preferred embodiment and cooperation detailed description, are described as follows:
Referring first to Fig. 1, in a preferred embodiment, disclosed lithium battery contains the present invention in structure:
One positive plate 1, an isolating membrane 2 and a negative plate 3, isolating membrane 2 therein adjacent to positive plate 1, and
Negative plate 3 is adjacent to isolating membrane 2, and therefore isolating membrane 2 separates positive plate 1 and negative plate 3 and makes both
Will not contact.There is between positive plate 1 and isolating membrane 2 one first accommodation space 41, and negative plate 3 with every
Then there is between film 2 one second accommodation space 42, this first accommodation space 41 and the second accommodation space
42 are filled by electrolyte.
In a preferred embodiment, positive plate 1 comprises a positive-pole base material 11 to the present invention and a positive pole applies
Layer 12, this positive pole coating 12 coats at least one side of positive-pole base material 11, and its composition comprises butadiene-benzene second
Alkene-methacrylate copolymer, and can further include lithium and cobalt oxides (licoo2), lithium cobalt nickel
Mn oxide (li1-u-v-wcounivmnwo2) (0 <u < 1,0 < v < 1,0 < w < 1) or iron lithium phosphate isoreactivity material,
And conductive carbon material, positive electrode binder and water or organic solvent.Wherein, conductive carbon material can for toner body,
Graphite, carbon fiber or carbon nanotube.Positive electrode binder can be polyvinylidene fluoride (pvdf) or carboxymethyl cellulose
Plain sodium (sodium carboxymthyl cellulose, cmc), and organic solvent is then n- N-methyl 2-pyrrolidone N-
(nmp).
Butadiene-styrene-methacrylate copolymer is the variant of butadiene-styrene rubber；Definite and
Speech, butadiene-styrene rubber is formed by styrene and polymerizing butadiene, and this case is then additionally using methacrylic acid alkane
Base ester is polymerized with styrene and butadiene, and the chemical structural formula of the monomer of its copolymer being formed comprises
(c6h6)x、(c8h8)yAnd (c4h5o2r)z, wherein x > 1；y>1；z>1；R be carbon number > 1 alkane chain.One relatively
In good embodiment, the chemical structural formula of this copolymer is:
-(c6h6)x-(c8h8)y-(c4h5o2r)z-
.Coating containing butadiene-styrene-methacrylate copolymer coated on positive-pole base material 11
, thus forming positive pole coating 12, this positive pole coating 12 can play the function of lifting lithium battery safety.Work as lithium
The battery impact such as be subject to external impacts, foreign body to pierce through and when so that structure has been damaged, its qualitative change first
To be impaired harm produce heat energy because of short circuit, temperature rises, and now contained by the positive pole coating 12 of positive plate 1
Butadiene-styrene-methacrylate copolymer can be because by thermal acceleration melting and expansion, Jin Erjiao
Turn to the material of tool high-ohmic, intercept and there are the other materials of electric conductivity, such as conductive carbon material, thus
Forming region open circuit.In other words, the present invention makes lithium battery through the special material contained by positive pole coating
Injured scope control, in injured scope itself, will not make whole lithium battery heat up because of short circuit comprehensively
Melt to comprehensive.Can automatically obtain under control in injured scope, unimpaired scope still can maintain
The running voltage and operation such as charge and discharge.
Compared to positive plate 1, negative plate 3 then can not use butadiene-styrene-methacrylate
Ester copolymer as one of coating material, and only select butadiene-styrene rubber, but negative pole also from coating butadiene-
Styrene-t alkyl ester copolymer is one of preferred embodiment of the present invention.Negative plate 3
Structure comprises a base material of cathode 31 and a negative pole coating 32, and can comprise as work in the middle of negative pole coating 32
The graphite system material with carbon element of property material, the sodium carboxymethyl cellulose as negative pole adhesive.Another in the present invention
In preferred embodiment, only positive plate 1 is used styrene-t alkyl ester copolymer as coating material
One of.
Material selection, positive-pole base material 11 and base material of cathode 31 for each composition assembly of lithium battery
Can be metallic membrane or other conductive material, in a preferred embodiment, positive-pole base material 11 can be aluminium foil,
Base material of cathode 31 is then Copper Foil；And in a further preferred embodiment, base material of cathode 31 can be changed to select graphite
.Then the plastic foil such as pe, pp may be selected positioned at the isolating membrane 2 between positive plate 1 and negative plate 3, its
Body has the structure of micro- porous, thus may be allowed to the electrolyte circulation of its both sides.The positive pole of lithium battery is born and can be made
With aluminium strip or nickel strap as terminal.And as being filled in the first accommodation space 41 and the second accommodation space 42
Electrolyte, then can select using lithium hexafluoro phosphate (lipf6), ethylene carbonate (ethylene
Carbonate, ec), Allyl carbonate (propylene carbonate, pc) and dimethyl carbonate
The mixture of (dimethyl carbonate, dmc), in a preferred embodiment, electrolyte comprises weight hundred
Divide the lipf of the ec, 5～20% pc, 10～40% dmc and remaining percentage ratio than 30～50%6.
Disclosed lithium battery in manufacture method, be generally speaking in advance make positive plate with
And negative plate, then both are carried out storehouse and winding with isolating membrane, then pass through typically known activation again and (change
Become), classification, packaging etc. complete after program.And wherein in order to control property and the safety of lithium battery, this
It is bright that in manufacture method, the making for pole piece is coated using special material, with realize high security and
The purpose of maintenance work ability.
The making of positive plate, in a preferred embodiment, comprises step:
1. sodium carboxymethyl cellulose is completely dissolved in percentage by weight with the ratio of percentage by weight 0.5～5%
In 99.5～95% water, form one first solution；2. by the first solution and active material, conductive carbon material
Mix to completely uniform, the percentage by weight of three is 15～70%:30～75%:0～10%, form one the
Two solution, active material can be selected for lithium and cobalt oxides, lithium cobalt nickel manganese oxide or iron lithium phosphate；
3. add the butadiene-styrene-methacrylic acid alkenyl esters of percentage by weight 0.2～6% in the second solution altogether
Polymers, forms one the 3rd solution；And
4. adjust the viscosity of the 3rd solution using the mode of Deca pure water, make viscosity be controlled to the model of 500～25000cps
Enclose, then coated the two sides of positive-pole base material (aluminium foil), then carry out one side baking, gained after baking
Positive pole coating painting again be 8～26mg/cm2, complete the making of positive plate.
The making of negative plate, in a preferred embodiment, comprises step:
1. sodium carboxymethyl cellulose is completely dissolved in total weight percent with the ratio of total weight percent 0.5-5%
In the water of 95-99.5%, form one the 4th solution；
2. the 4th solution is mixed to completely uniform, the weight percent of three with the active material of negative pole, conductive carbon material
Ratio for 25～70%:30～70%:0～5%, forms one the 5th solution, and active material can be selected for graphite system carbon materials
Material；
3. add the butadiene-styrene-methacrylic acid alkenyl esters of percentage by weight 0.2～3% in the 5th solution altogether
Polymers, forms one the 6th solution；And
4. adjust the viscosity of the 6th solution using the mode of Deca pure water, make viscosity be controlled to the model of 250～15000cps
Enclose, then coated the two sides of base material of cathode (Copper Foil), then carry out one side baking, gained after baking
Negative pole coating painting again be 3～16mg/cm2, complete the making of negative plate.
The aforementioned positive plate made and negative plate system and isolating membrane are according to winding or lamination process, and add
Enter electrolyte, be made as lithium battery secondary cell (use of can repeatedly charging), then carry out safety test.This
The made lithium battery of invention can be formed because of the quick coking of the special material contained by positive plate in the position being punctured
Insulating barrier, does not form real internal short-circuit；This insulating barrier not only can protect point of puncture, and assign simultaneously
Battery is given still to be capable of the characteristic of multiple discharge and recharge after piercing.Refer to Fig. 2 and table 1, lithium battery is
Tested needle-penetration when 90 seconds, but it does not therefore burn or damages completely, its battery bulk temperature
Ascensional range is extremely low, maximum temperature not less than 40 DEG C, and can maintain the electricity of 3.2v within the time of two weeks
Pressure.In addition refer to Fig. 3, disclosed lithium battery after pierced, in a test result, its
Still carry out 15 completely discharge and recharge and undamped signs, then just start progressively to decay, provable impaired
Lithium battery afterwards is still provided that the characteristic persistently using.
(table 1)
The present invention discloses a kind of lithium battery and its copolymer of positive pole coating in detail, and it is in the middle of structure
Positive plate there is the positive pole coating comprising butadiene-styrene-methacrylate copolymer, be one
Kind it is provided that the material of regional protection, the infringement such as it can make lithium battery being punctured by foreign body, external force collision
When, because structure accelerates melting and expanded by heating in the range of affected area, and so that resistance is increased and form open circuit
, maintain the integrity in the intact region of lithium battery and the working condition not being short-circuited, thereby avoid lithium battery
Because of internal short-circuit, thus temperature quickly rises, in reach material burning-point or disintegrate point and lead to cells burst or
The probability of blast.Based on above-mentioned security feature, for summary, the present invention is that one kind has Gao Jing really
Lithium battery and its copolymer of positive pole coating that Ji is worth.
Above is only presently preferred embodiments of the present invention, be not used for limiting the scope of present invention enforcement,
All impartial changes done according to the shape described in scope of the invention as claimed, construction, feature and spirit with repair
Decorations, all should be included in scope of the presently claimed invention.
Claims (10)
1. a kind of lithium battery is it is characterised in that its structure comprises:
One positive plate, it comprises a positive-pole base material and a positive pole coating, and this positive pole coating comprises fourth two
Alkene-styrene-t alkyl ester copolymer；
One isolating membrane, it is adjacent to this positive plate, and has one first accommodating sky and this positive plate between
Between；
One negative plate, it is adjacent to this isolating membrane, and has one second accommodating sky and this isolating membrane between
Between；And
One electrolyte, is arranged at this first accommodation space and this second accommodation space.
2. lithium battery as claimed in claim 1 is it is characterised in that wherein this positive pole coating further includes lithium cobalt
Oxide (licoo2), lithium cobalt nickel manganese oxide (li1-x-y-zcoxniymnzo2) and iron lithium phosphate (lifepo4) institute
Group's one of which of composition.
3. lithium battery as claimed in claim 1 is it is characterised in that wherein this positive pole coating further includes one and leads
Electrical carbon material.
4. lithium battery as claimed in claim 1 is it is characterised in that wherein this positive pole coating is just further including one
Pole adhesive, this positive electrode binder is sodium carboxymethyl cellulose.
5. lithium battery as claimed in claim 1 it is characterised in that wherein this positive pole coating further include water or
One organic solvent, this organic solvent is n- N-methyl 2-pyrrolidone N-.
6. lithium battery as claimed in claim 1 is it is characterised in that wherein this negative plate comprises a negative pole base
Material and a negative pole coating, this base material of cathode is Copper Foil.
7. lithium battery as claimed in claim 6 is it is characterised in that wherein this negative pole coating comprises butylbenzene rubber
Glue and graphite system material with carbon element.
8. lithium battery as claimed in claim 6 is it is characterised in that wherein this negative pole coating comprises a negative pole
Adhesive, this negative pole adhesive is sodium carboxymethyl cellulose.
9. lithium battery as claimed in claim 1 is it is characterised in that wherein this electrolyte comprises hexafluorophosphoric acid
Lithium (lipf6), ethylene carbonate (ethylene carbonate, ec), Allyl carbonate (propylene
Carbonate, pc) and dimethyl carbonate (dimethyl carbonate, dmc).
10. a kind of copolymer of lithium battery anode coating is it is characterised in that the chemical structural formula of monomer comprises
(c6h6)x、(c8h8)yAnd (c4h5o2r)z, wherein x > 1, y > 1, z > 1, and r be carbon number > 1 alkane chain.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| TW104123824A TWI618287B (en) | 2015-07-23 | 2015-07-23 | Copolymer of lithium battery and its positive electrode coating |
| TW104123824 | 2015-07-23 |
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| Publication Number | Publication Date |
|---|---|
| CN106374112A true CN106374112A (en) | 2017-02-01 |
Family
ID=57880927
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510464195.XA Pending CN106374112A (en) | 2015-07-23 | 2015-07-31 | Lithium battery and positive electrode coating copolymer thereof |
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| Country | Link |
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| CN (1) | CN106374112A (en) |
| TW (1) | TWI618287B (en) |
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| CN108630888A (en) * | 2017-03-22 | 2018-10-09 | 丰田自动车株式会社 | The manufacturing method of negative electrode for nonaqueous secondary battery and the manufacturing method of nonaqueous electrolytic solution secondary battery |
| CN113728504A (en) * | 2020-12-09 | 2021-11-30 | 宁德新能源科技有限公司 | Polymer binder, laminated porous film, battery, and electronic device |
| WO2022165780A1 (en) * | 2021-02-06 | 2022-08-11 | 宁德时代新能源科技股份有限公司 | Secondary battery, and battery module, battery pack, and device comprising same |
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| US20110129731A1 (en) * | 2008-08-05 | 2011-06-02 | Yasuhiro Wakizaka | Electrode for lithium-ion secondary battery |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108630888A (en) * | 2017-03-22 | 2018-10-09 | 丰田自动车株式会社 | The manufacturing method of negative electrode for nonaqueous secondary battery and the manufacturing method of nonaqueous electrolytic solution secondary battery |
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| CN113728504A (en) * | 2020-12-09 | 2021-11-30 | 宁德新能源科技有限公司 | Polymer binder, laminated porous film, battery, and electronic device |
| WO2022120654A1 (en) * | 2020-12-09 | 2022-06-16 | 宁德新能源科技有限公司 | Polymer binder, laminated porous membrane, battery, and electronic apparatus |
| CN113728504B (en) * | 2020-12-09 | 2024-02-27 | 宁德新能源科技有限公司 | Polymer binder, laminated porous film, battery, and electronic device |
| WO2022165780A1 (en) * | 2021-02-06 | 2022-08-11 | 宁德时代新能源科技股份有限公司 | Secondary battery, and battery module, battery pack, and device comprising same |
| US11646455B2 (en) | 2021-02-06 | 2023-05-09 | Contemporary Amperex Technology Co., Limited | Secondary battery, and battery module, battery pack, and device having same |
Also Published As
| Publication number | Publication date |
|---|---|
| TWI618287B (en) | 2018-03-11 |
| TW201705590A (en) | 2017-02-01 |
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Application publication date: 20170201 |