CN107482250B - A kind of dynamic lithium battery of containing graphene - Google Patents
A kind of dynamic lithium battery of containing graphene Download PDFInfo
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- CN107482250B CN107482250B CN201710534875.3A CN201710534875A CN107482250B CN 107482250 B CN107482250 B CN 107482250B CN 201710534875 A CN201710534875 A CN 201710534875A CN 107482250 B CN107482250 B CN 107482250B
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 135
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 135
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 35
- 239000000654 additive Substances 0.000 claims abstract description 130
- 230000000996 additive effect Effects 0.000 claims abstract description 130
- 239000007788 liquid Substances 0.000 claims abstract description 58
- 239000002994 raw material Substances 0.000 claims abstract description 48
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 28
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 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 claims abstract description 14
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 14
- 239000010452 phosphate Substances 0.000 claims abstract description 14
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 14
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims abstract description 12
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 claims abstract description 11
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims abstract description 11
- VUPKGFBOKBGHFZ-UHFFFAOYSA-N dipropyl carbonate Chemical compound CCCOC(=O)OCCC VUPKGFBOKBGHFZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 claims abstract description 11
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229940090181 propyl acetate Drugs 0.000 claims abstract description 11
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims abstract description 11
- SPEUIVXLLWOEMJ-UHFFFAOYSA-N 1,1-dimethoxyethane Chemical compound COC(C)OC SPEUIVXLLWOEMJ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000003792 electrolyte Substances 0.000 claims description 33
- -1 sucrose ester Chemical class 0.000 claims description 27
- 238000002360 preparation method Methods 0.000 claims description 19
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 18
- 239000000843 powder Substances 0.000 claims description 12
- 239000011347 resin Substances 0.000 claims description 9
- 229920005989 resin Polymers 0.000 claims description 9
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims description 8
- KBIWNQVZKHSHTI-UHFFFAOYSA-N 4-n,4-n-dimethylbenzene-1,4-diamine;oxalic acid Chemical compound OC(=O)C(O)=O.CN(C)C1=CC=C(N)C=C1 KBIWNQVZKHSHTI-UHFFFAOYSA-N 0.000 claims description 8
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 8
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Natural products OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 8
- 150000002148 esters Chemical class 0.000 claims description 8
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 claims description 6
- 229930006000 Sucrose Natural products 0.000 claims description 6
- 150000001336 alkenes Chemical class 0.000 claims description 6
- 238000007334 copolymerization reaction Methods 0.000 claims description 6
- 229940093476 ethylene glycol Drugs 0.000 claims description 6
- 229920002857 polybutadiene Polymers 0.000 claims description 6
- 229950008882 polysorbate Drugs 0.000 claims description 6
- 229920000136 polysorbate Polymers 0.000 claims description 6
- 229920002635 polyurethane Polymers 0.000 claims description 6
- 239000004814 polyurethane Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 239000005720 sucrose Substances 0.000 claims description 6
- HQPMKSGTIOYHJT-UHFFFAOYSA-N ethane-1,2-diol;propane-1,2-diol Chemical compound OCCO.CC(O)CO HQPMKSGTIOYHJT-UHFFFAOYSA-N 0.000 claims description 4
- 229910002804 graphite Inorganic materials 0.000 claims description 4
- 239000010439 graphite Substances 0.000 claims description 4
- 229920001993 poloxamer 188 Polymers 0.000 claims description 4
- 239000004925 Acrylic resin Substances 0.000 claims description 3
- 229920000178 Acrylic resin Polymers 0.000 claims description 3
- DVLFYONBTKHTER-UHFFFAOYSA-N 3-(N-morpholino)propanesulfonic acid Chemical compound OS(=O)(=O)CCCN1CCOCC1 DVLFYONBTKHTER-UHFFFAOYSA-N 0.000 claims 1
- 150000002596 lactones Chemical class 0.000 claims 1
- 230000000052 comparative effect Effects 0.000 description 25
- 239000012530 fluid Substances 0.000 description 21
- 238000002347 injection Methods 0.000 description 21
- 239000007924 injection Substances 0.000 description 21
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 15
- 229910001416 lithium ion Inorganic materials 0.000 description 15
- 230000032683 aging Effects 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 10
- 238000007796 conventional method Methods 0.000 description 10
- 238000007872 degassing Methods 0.000 description 10
- 238000007789 sealing Methods 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 description 7
- 239000002253 acid Substances 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910001290 LiPF6 Inorganic materials 0.000 description 3
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 description 3
- XOBKSJJDNFUZPF-UHFFFAOYSA-N Methoxyethane Chemical compound CCOC XOBKSJJDNFUZPF-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—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
- H01M10/0568—Liquid materials characterised by the solutes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a kind of dynamic lithium batteries of containing graphene, liquid is electrolysed including electrode group and dynamic lithium battery, the electrode group and dynamic lithium battery electrolysis liquid are sealed in battery case, the electrode group includes anode, cathode and diaphragm, the dynamic lithium battery is electrolysed liquid, as unit of parts by weight, including following raw material: 2-6 parts of lithium hexafluoro phosphate, 26-40 parts of methyl ethyl carbonate, 16-25 parts of dimethyl carbonate, 8-15 parts of butylene carbonate, 6-12 parts of dipropyl carbonate, 5-8 parts of Ethyl formate, 4-9 parts of propyl acetate, 1, 10-14 parts of 2- dimethoxy-ethane, 0.6-1 parts of modified graphene, 0.5-0.8 parts of additive a.Excellent using the high and low temperature performance and cycle performance of dynamic lithium battery made from dynamic lithium battery provided by the invention electrolysis liquid, dynamic lithium battery electrolysis liquid provided by the invention is worthy of popularization.
Description
[technical field]
The invention belongs to battery technology fields, and in particular to a kind of dynamic lithium battery of containing graphene.
[background technique]
In recent years, with the rapid development of lithium electricity industry, lithium ion battery starts to enter electric vehicle and large-scale shifting successively
Dynamic power supply application field, but lead-acid battery still occupies leading position at present.Anode material for lithium-ion batteries is usually cobalt acid lithium, manganese
The transition metal oxide of sour lithium, lithium nickelate and the other elements of all kinds of doping.For power battery, LiMn2O4 is gradually played
Its advantage out, becomes one of positive electrode of mainstream.Lithium-ion battery electrolytes occupy critically important position in lithium ion battery
It sets, it directly affects the electrical property of lithium ion battery.The electrolyte composition main electrolyte salt and solvent of lithium ion battery at present
Composition, wherein solvent generally uses carbonates mixed solvent such as ethylene carbonate EC, propylene carbonate ester PC, methyl ethyl carbonate
EMC, dimethyl carbonate DMC, diethyl carbonate DEC etc., common electrolytic salt are lithium hexafluoro phosphate LiPF6。
Lithium ion battery has many advantages, such as voltage platform height, energy without memory, is widely applied.But lithium ion simultaneously
One of an important factor for application range of battery also receives the limitation of some conditions, and the environment temperature of such as application is wherein.
And the cycle performance of current lithium manganate battery is also poor, remains to be further improved.
The lithium ion battery of current battery manufacturer production relatively mostly uses LiPF6The electrolyte of/EC+DMC+EMC composition, wherein
The volume ratio of EC, DMC and EMC are EC:DMC:EMC=1:1:1, though the electrolyte system has preferable security performance and activity
Matter content plays, but low and high temperature cycle performance is not ideal enough, when especially for use in the lithium ion battery of LiMn2O4 system,
High temp effect performance is poor, is no longer satisfied the needs of dynamic lithium battery, is further improved.
[summary of the invention]
The technical problem to be solved in the present invention is to provide a kind of dynamic lithium batteries of containing graphene, to solve existing lithium ion
Battery uses LiPF6The electrolyte of/EC+DMC+EMC composition, low and high temperature cycle performance is not ideal enough, and high temp effect performance is compared
Difference is no longer satisfied the problems such as needs of dynamic lithium battery.
In order to solve the above technical problems, the invention adopts the following technical scheme:
A kind of dynamic lithium battery of containing graphene, including electrode group and dynamic lithium battery are electrolysed liquid, the electrode group and dynamic
Power lithium battery electrolytes are sealed in battery case, and the electrode group includes the positive electrode, the negative electrode and the separator, the power lithium cell electric
Liquid is solved, as unit of parts by weight, including following raw material: 2-6 parts of lithium hexafluoro phosphate, 26-40 parts of methyl ethyl carbonate, dimethyl carbonate
16-25 parts, 8-15 parts of butylene carbonate, 6-12 parts of dipropyl carbonate, 5-8 parts of Ethyl formate, 4-9 parts of propyl acetate, 1,2- bis-
10-14 parts of Ethyl Methyl Ether, 0.6-1 parts of modified graphene and 0.5-0.8 parts of additive a；
The preparation method of the modified graphene, comprising the following steps: S1: by graphene magnetic field strength be 4800-
7000GS, ultrasonic power 220-580W, temperature are 40-56 DEG C, and revolving speed is to stir 15-42min under 200-300r/min,
Graphene energy powder is made；
S2: being added neopelex into graphene energy powder made from step S1, is 52-75 in temperature
DEG C, revolving speed is modified 1-2h under 90-150r/min, and modified graphene is made；
The additive a is as unit of parts by weight, including following raw material: 4-10 parts of glycerin monostearate, sucrose ester 2-4
Part, 1-2 parts of Pluronic F68 and 3-5 parts of polysorbate.
Further, the dynamic lithium battery electrolysis liquid further includes following raw material: additive b as unit of parts by weight
0.3-0.5 parts, the additive b is as unit of parts by weight, including following raw material: 7-15 parts of ethyleneglycol dimethyacrylate and
2-6 parts of tetramethyl siloxanes.
Further, the dynamic lithium battery electrolysis liquid further includes following raw material: additive c as unit of parts by weight
0.2-0.4 parts, the additive c is as unit of parts by weight, including following raw material: acrylate modified butadiene resin 12-20
Part and 4-12 parts of acrylic resin polyurethane copolymerization resin.
Further, the dynamic lithium battery electrolysis liquid further includes following raw material: additive d as unit of parts by weight
0.2-0.3 parts, the additive d is as unit of parts by weight, including following raw material: ethanedioic acid two (Butoxyethoxy second) ester 8-
12 parts, 4-10 parts of vinylene carbonate and 5-9 parts of 1,3-propane sultone.
Further, the dynamic lithium battery electrolysis liquid further includes following raw material: additive e as unit of parts by weight
0.3-0.6 parts, the additive e is 1,3- diketone.
Further, the preparation method of the dynamic lithium battery electrolysis liquid, comprising the following steps:
(1) by methyl ethyl carbonate, dimethyl carbonate, butylene carbonate and 1 in closed environment, 2- dimethoxy-ethane is equal
Even mixing；
(2) lithium hexafluoro phosphate, modified graphene, additive a, additive b and additive c is then added to be sufficiently mixed；
(3) dipropyl carbonate, Ethyl formate, propyl acetate, additive d and additive e are eventually adding to be uniformly mixed, is made
Dynamic lithium battery is electrolysed liquid.
The invention has the following advantages:
(1) modified graphene, additive a, additive b, additive c, additive d, the effect difference of additive e are as follows:
1) graphene by be modified, become hydrophobicity, be conducive to it is compatible with organic solvent, to improve dynamic lithium battery
Performance；
2) addition of the additive a reduces the surface tension of electrolyte of lithium-ion secondary battery, effectively improves positive and negative
Pole piece and diaphragm infiltrate the absorption of electrolyte, so that electrolyte is rapidly achieved the state of stable and uniform in the battery, can be improved
The cycle life of dynamic lithium battery.
3) additive b forms layer protecting film in positive electrode surface, reduces electrolyte in positive table during initial charge
Face, which is decomposed, produces gas, and in subsequent charge and discharge process, is able to suppress the Mn in positive active material2+The dissolution of ion,
Improve the high-temperature behavior of lithium manganate battery.
4) additive c can make negative terminal surface form layer protecting film；
5) the electrolyte cryogenic property of dynamic lithium battery can be improved in additive d, selects two (Butoxyethoxy of ethanedioic acid
Second) ester, vinylene carbonate, 1,3-propane sultone as the raw material for preparing that can reduce temperature additive d, electrolyte adds
Add the decomposition voltage that can effectively improve electrolyte after agent d, passivating film can be formed on composite graphite negative electrode surface, also had to anode
Preferable oxidation stability, the effective working performance improved under electrolyte low temperature, extends longevity time of dynamic lithium battery entirety
Life (improves the storage service life of battery)；
6) additive e can be complexed with lithium ion, carry out ion transmission, so as to eliminate dynamic lithium battery electrolysis liquid
It is due to the acidic materials that lithium hexafluoro phosphate hydrolyzes and generates, to improve the performance of dynamic lithium battery.
Modified graphene, additive a, additive b, additive it can be seen from embodiment 3 and the data of comparative example 1-7
C, additive d, additive e addition simultaneously prepare dynamic lithium battery electrolysis liquid, using battery made of the above electrolyte, modified stone
Black alkene, additive a, additive b, additive c, additive d, additive e produce synergistic effect, significantly improve power lithium battery
The high and low temperature performance and cycle performance in pond.
(2) the high and low temperature performance of dynamic lithium battery made from liquid is electrolysed using dynamic lithium battery provided by the invention and followed
Ring function admirable, dynamic lithium battery electrolysis liquid provided by the invention are worthy of popularization.
[specific embodiment]
To facilitate a better understanding of the present invention, it is illustrated by the following examples, these examples belong to protection of the invention
Range, but do not limit the scope of the invention.
In embodiment, the dynamic lithium battery, including electrode group and dynamic lithium battery are electrolysed liquid, the electrode group and dynamic
Power lithium battery electrolytes are sealed in battery case, and the electrode group includes the positive electrode, the negative electrode and the separator, the power lithium cell electric
Liquid is solved, as unit of parts by weight, including following raw material: 2-6 parts of lithium hexafluoro phosphate, 26-40 parts of methyl ethyl carbonate, dimethyl carbonate
16-25 parts, 8-15 parts of butylene carbonate, 6-12 parts of dipropyl carbonate, 5-8 parts of Ethyl formate, 4-9 parts of propyl acetate, 1,2- bis-
10-14 parts of Ethyl Methyl Ether, 0.6-1 parts of modified graphene, 0.5-0.8 parts of additive a, 0.3-0.5 parts of additive b, addition
0.2-0.4 parts of agent c, 0.2-0.3 parts of additive d and 0.3-0.6 parts of additive e；
The preparation method of the modified graphene, comprising the following steps: S1: by graphene magnetic field strength be 4800-
7000GS, ultrasonic power 220-580W, temperature are 40-56 DEG C, and revolving speed is to stir 15-42min under 200-300r/min,
Graphene energy powder is made；
S2: being added neopelex into graphene energy powder made from step S1, is 52-75 in temperature
DEG C, revolving speed is modified 1-2h under 90-150r/min, and modified graphene is made；
The additive a is as unit of parts by weight, including following raw material: 4-10 parts of glycerin monostearate, sucrose ester 2-4
Part, 1-2 parts of Pluronic F68 and 3-5 parts of polysorbate；
The additive b is as unit of parts by weight, including following raw material: 7-15 parts of ethyleneglycol dimethyacrylate and four
2-6 parts of methylsiloxane；
The additive c is as unit of parts by weight, including following raw material: acrylate modified butadiene resin 12-20 parts
With 4-12 parts of acrylic resin polyurethane copolymerization resin；
The additive d is as unit of parts by weight, including following raw material: ethanedioic acid two (Butoxyethoxy second) ester 8-12
Part, 4-10 parts of vinylene carbonate and 5-9 parts of 1,3-propane sultone；
The additive e is 1,3- diketone.
The preparation method of the dynamic lithium battery electrolysis liquid, comprising the following steps:
(1) by methyl ethyl carbonate, dimethyl carbonate, butylene carbonate and 1 in closed environment, 2- dimethoxy-ethane is equal
Even mixing；
(2) lithium hexafluoro phosphate, modified graphene, additive a, additive b and additive c is then added to be sufficiently mixed；
(3) dipropyl carbonate, Ethyl formate, propyl acetate, additive d and additive e are eventually adding to be uniformly mixed, is made
Dynamic lithium battery is electrolysed liquid.
Below by more specifically examples illustrate the present invention.
Embodiment 1
A kind of dynamic lithium battery of containing graphene, including electrode group and dynamic lithium battery are electrolysed liquid, the electrode group and dynamic
Power lithium battery electrolytes are sealed in battery case, and the electrode group includes the positive electrode, the negative electrode and the separator, the power lithium cell electric
Solve liquid, as unit of parts by weight, including following raw material: 4 parts of lithium hexafluoro phosphate, 34 parts of methyl ethyl carbonate, 20 parts of dimethyl carbonate,
12 parts of butylene carbonate, 7 parts of Ethyl formate, 6 parts of propyl acetate, 12 parts of 1,2- dimethoxy-ethane, changes 10 parts of dipropyl carbonate
Property 0.8 part of graphene, 0.7 part of additive a, 0.4 part of additive b, 0.3 part of additive c, 0.2 part of additive d and additive
0.5 part of e；
The preparation method of the modified graphene, comprising the following steps: S1: by graphene magnetic field strength be 6000GS,
Ultrasonic power is 400W, and temperature is 50 DEG C, and revolving speed is to stir 30min under 200r/min, and graphene energy powder is made；
S2: being added neopelex into graphene energy powder made from step S1, is 63 DEG C in temperature, turns
Speed is modified 1.5h under 120r/min, and modified graphene is made；
The additive a is as unit of parts by weight, including following raw material: 7 parts of glycerin monostearate, gathers 3 parts of sucrose ester
Ethylene oxide -1.6-2 parts of poiyoxypropylene copolymer and 4 parts of polysorbate；
The additive b is as unit of parts by weight, including following raw material: 12 parts of ethyleneglycol dimethyacrylate and tetramethyl
4 parts of radical siloxane；
The additive c is as unit of parts by weight, including following raw material: 16 parts of acrylate modified butadiene resin and third
8 parts of resin of olefin(e) acid resin polyurethane copolymerization；
The additive d is as unit of parts by weight, including following raw material: ethanedioic acid two (Butoxyethoxy second) ester 10
Part, 8 parts of vinylene carbonate and 7 parts of 1,3-propane sultone；
The additive e is 1,3- diketone.
The preparation method of the dynamic lithium battery electrolysis liquid, comprising the following steps:
(1) by methyl ethyl carbonate, dimethyl carbonate, butylene carbonate and 1 in closed environment, 2- dimethoxy-ethane is equal
Even mixing；
(2) lithium hexafluoro phosphate, modified graphene, additive a, additive b and additive c is then added to be sufficiently mixed；
(3) dipropyl carbonate, Ethyl formate, propyl acetate, additive d and additive e are eventually adding to be uniformly mixed, is made
Dynamic lithium battery is electrolysed liquid.
This 20 pieces of batteries are injected separately into this in constant temperature and humidity room by 1665132 batteries for randomly selecting 20 non-fluid injections
The dynamic lithium battery that embodiment provides is electrolysed liquid, according to a conventional method by the battery of fluid injection carry out aging, chemical conversion, degasification, sealing,
Dynamic lithium battery is made in partial volume.
Embodiment 2
A kind of dynamic lithium battery of containing graphene, including electrode group and dynamic lithium battery are electrolysed liquid, the electrode group and dynamic
Power lithium battery electrolytes are sealed in battery case, and the electrode group includes the positive electrode, the negative electrode and the separator, the power lithium cell electric
Liquid is solved, as unit of parts by weight, including following raw material: 2.2 parts of lithium hexafluoro phosphate, 28 parts of methyl ethyl carbonate, dimethyl carbonate 16
Part, 8 parts of butylene carbonate, 6 parts of dipropyl carbonate, 5 parts of Ethyl formate, 4 parts of propyl acetate, 10 parts of 1,2- dimethoxy-ethane,
0.6 part of modified graphene, 0.5 part of additive a, 0.3 part of additive b, 0.2 part of additive c, 0.2 part of additive d and addition
0.3 part of agent e；
The preparation method of the modified graphene, comprising the following steps: S1: by graphene magnetic field strength be 4800GS,
Ultrasonic power is 220W, and temperature is 40 DEG C, and revolving speed is to stir 42min under 200r/min, and graphene energy powder is made；
S2: being added neopelex into graphene energy powder made from step S1, is 52 DEG C in temperature, turns
Speed is modified 2h under 90r/min, and modified graphene is made；
The additive a is as unit of parts by weight, including following raw material: 4 parts of glycerin monostearate, gathers 2 parts of sucrose ester
1 part and 3 parts of polysorbate of ethylene oxide-poiyoxypropylene copolymer；
The additive b is as unit of parts by weight, including following raw material: 7 parts of ethyleneglycol dimethyacrylate and tetramethyl
2 parts of radical siloxane；
The additive c is as unit of parts by weight, including following raw material: 12 parts of acrylate modified butadiene resin and third
4 parts of resin of olefin(e) acid resin polyurethane copolymerization；
The additive d is as unit of parts by weight, including following raw material: 8 parts of ethanedioic acid two (Butoxyethoxy second) ester,
4 parts and 5 parts of 1,3-propane sultone of vinylene carbonate；
The additive e is 1,3- diketone.
The preparation method of dynamic lithium battery electrolysis liquid provided in this embodiment is the same as embodiment 1.
This 20 pieces of batteries are injected separately into this in constant temperature and humidity room by 1665132 batteries for randomly selecting 20 non-fluid injections
The dynamic lithium battery that embodiment provides is electrolysed liquid, according to a conventional method by the battery of fluid injection carry out aging, chemical conversion, degasification, sealing,
Dynamic lithium battery is made in partial volume.
Embodiment 3
A kind of dynamic lithium battery of containing graphene, including electrode group and dynamic lithium battery are electrolysed liquid, the electrode group and dynamic
Power lithium battery electrolytes are sealed in battery case, and the electrode group includes the positive electrode, the negative electrode and the separator, the power lithium cell electric
Liquid is solved, as unit of parts by weight, including following raw material: 5.8 parts of lithium hexafluoro phosphate, 39 parts of methyl ethyl carbonate, dimethyl carbonate 24
Part, 15 parts of butylene carbonate, 12 parts of dipropyl carbonate, 8 parts of Ethyl formate, 9 parts of propyl acetate, 1,2- dimethoxy-ethane 14
Part, 0.9 part of modified graphene, 0.8 part of additive a, 0.5 part of additive b, 0.4 part of additive c, 0.3 part of additive d and
0.6 part of additive e；
The preparation method of the modified graphene, comprising the following steps: S1: by graphene magnetic field strength be 7000GS,
Ultrasonic power is 580W, and temperature is 56 DEG C, and revolving speed is to stir 15min under 300r/min, and graphene energy powder is made；
S2: being added neopelex into graphene energy powder made from step S1, is 75 DEG C in temperature, turns
Speed is modified 1h under 150r/min, and modified graphene is made；
The additive a is as unit of parts by weight, including following raw material: 10 parts of glycerin monostearate, 4 parts of sucrose ester,
2 parts and 5 parts of polysorbate of Pluronic F68；
The additive b is as unit of parts by weight, including following raw material: 15 parts of ethyleneglycol dimethyacrylate and tetramethyl
6 parts of radical siloxane；
The additive c is as unit of parts by weight, including following raw material: 20 parts of acrylate modified butadiene resin and third
12 parts of resin of olefin(e) acid resin polyurethane copolymerization；
The additive d is as unit of parts by weight, including following raw material: ethanedioic acid two (Butoxyethoxy second) ester 12
Part, 10 parts of vinylene carbonate and 9 parts of 1,3-propane sultone；
The additive e is 1,3- diketone.
The preparation method of dynamic lithium battery electrolysis liquid provided in this embodiment is the same as embodiment 1.
This 20 pieces of batteries are injected separately into this in constant temperature and humidity room by 1665132 batteries for randomly selecting 20 non-fluid injections
The dynamic lithium battery that embodiment provides is electrolysed liquid, according to a conventional method by the battery of fluid injection carry out aging, chemical conversion, degasification, sealing,
Dynamic lithium battery is made in partial volume.
Comparative example 1
Compared with Example 3, unlike having only: preparing and lack modified graphene, addition in the raw material of dynamic lithium battery
Agent a, additive b, additive c, additive d and additive e.
The preparation method for the dynamic lithium battery electrolysis liquid that this comparative example provides is the same as embodiment 3.
This 20 pieces of batteries are injected separately into this in constant temperature and humidity room by 1665132 batteries for randomly selecting 20 non-fluid injections
The dynamic lithium battery that comparative example provides is electrolysed liquid, according to a conventional method by the battery of fluid injection carry out aging, chemical conversion, degasification, sealing,
Dynamic lithium battery is made in partial volume.
Comparative example 2
Compared with Example 3, unlike having only: preparing and lack modified graphene in the raw material of dynamic lithium battery.
The preparation method for the dynamic lithium battery electrolysis liquid that this comparative example provides is the same as embodiment 3.
This 20 pieces of batteries are injected separately into this in constant temperature and humidity room by 1665132 batteries for randomly selecting 20 non-fluid injections
The dynamic lithium battery that comparative example provides is electrolysed liquid, according to a conventional method by the battery of fluid injection carry out aging, chemical conversion, degasification, sealing,
Dynamic lithium battery is made in partial volume.
Comparative example 3
Compared with Example 3, unlike having only: preparing and lack additive a in the raw material of dynamic lithium battery.
The preparation method for the dynamic lithium battery electrolysis liquid that this comparative example provides is the same as embodiment 3.
This 20 pieces of batteries are injected separately into this in constant temperature and humidity room by 1665132 batteries for randomly selecting 20 non-fluid injections
The dynamic lithium battery that comparative example provides is electrolysed liquid, according to a conventional method by the battery of fluid injection carry out aging, chemical conversion, degasification, sealing,
Dynamic lithium battery is made in partial volume.
Comparative example 4
Compared with Example 3, unlike having only: preparing and lack additive b in the raw material of dynamic lithium battery.
The preparation method for the dynamic lithium battery electrolysis liquid that this comparative example provides is the same as embodiment 3.
This 20 pieces of batteries are injected separately into this in constant temperature and humidity room by 1665132 batteries for randomly selecting 20 non-fluid injections
The dynamic lithium battery that comparative example provides is electrolysed liquid, according to a conventional method by the battery of fluid injection carry out aging, chemical conversion, degasification, sealing,
Dynamic lithium battery is made in partial volume.
Comparative example 5
Compared with Example 3, unlike having only: preparing and lack additive c in the raw material of dynamic lithium battery.
The preparation method for the dynamic lithium battery electrolysis liquid that this comparative example provides is the same as embodiment 3.
This 20 pieces of batteries are injected separately into this in constant temperature and humidity room by 1665132 batteries for randomly selecting 20 non-fluid injections
The dynamic lithium battery that comparative example provides is electrolysed liquid, according to a conventional method by the battery of fluid injection carry out aging, chemical conversion, degasification, sealing,
Dynamic lithium battery is made in partial volume.
Comparative example 6
Compared with Example 3, unlike having only: preparing and lack additive d in the raw material of dynamic lithium battery.
The preparation method for the dynamic lithium battery electrolysis liquid that this comparative example provides is the same as embodiment 3.
This 20 pieces of batteries are injected separately into this in constant temperature and humidity room by 1665132 batteries for randomly selecting 20 non-fluid injections
The dynamic lithium battery that comparative example provides is electrolysed liquid, according to a conventional method by the battery of fluid injection carry out aging, chemical conversion, degasification, sealing,
Dynamic lithium battery is made in partial volume.
Comparative example 7
Compared with Example 3, unlike having only: preparing and lack additive e in the raw material of dynamic lithium battery.
The preparation method for the dynamic lithium battery electrolysis liquid that this comparative example provides is the same as embodiment 3.
This 20 pieces of batteries are injected separately into this in constant temperature and humidity room by 1665132 batteries for randomly selecting 20 non-fluid injections
The dynamic lithium battery that comparative example provides is electrolysed liquid, according to a conventional method by the battery of fluid injection carry out aging, chemical conversion, degasification, sealing,
Dynamic lithium battery is made in partial volume.
For convenient for comparing, the intercell used in above-described embodiment 1-3 and comparative example 1-7 is referred both to a collection of homotype number
The battery of (1665132S), described same a batch refer to the preamble production technology of this batch of battery all, and it is unique unlike
The electrolyte injected in fluid injection process is different.In the battery of the model, cathode is composite graphite, just extremely LiMn2O4.
Embodiment 1-3 and comparative example the 1-7 dynamic lithium battery made are subjected to 55 DEG C of high temperature, 1C electric discharge respectively, -20 DEG C,
1C electric discharge, -35 DEG C, 0.2C electric discharge, room temperature (25 DEG C) 1C loop test, 55 DEG C of high temperature, 1C loop test, test result is as follows table
It is shown.
As seen from the above table: (1) can be seen that by the test result of upper table using power lithium cell electric provided by the invention
High and low temperature performance and the cycle performance for solving dynamic lithium battery made from liquid are excellent, and dynamic lithium battery provided by the invention is electrolysed liquid
It is worthy of popularization.
(2) modified graphene, additive a, additive b, additive c, additive d, the effect difference of additive e are as follows:
1) graphene by be modified, become hydrophobicity, be conducive to it is compatible with organic solvent, to improve dynamic lithium battery
Performance；
2) addition of the additive a reduces the surface tension of electrolyte of lithium-ion secondary battery, effectively improves positive and negative
Pole piece and diaphragm infiltrate the absorption of electrolyte, so that electrolyte is rapidly achieved the state of stable and uniform in the battery, can be improved
The cycle life of dynamic lithium battery.
3) additive b forms layer protecting film in positive electrode surface, reduces electrolyte in positive table during initial charge
Face, which is decomposed, produces gas, and in subsequent charge and discharge process, is able to suppress the Mn in positive active material2+The dissolution of ion,
Improve the high-temperature behavior of lithium manganate battery.
4) additive c can make negative terminal surface form layer protecting film；
5) the electrolyte cryogenic property of dynamic lithium battery can be improved in additive d, selects two (Butoxyethoxy of ethanedioic acid
Second) ester, vinylene carbonate, 1,3-propane sultone as the raw material for preparing that can reduce temperature additive d, electrolyte adds
Add the decomposition voltage that can effectively improve electrolyte after agent d, passivating film can be formed on composite graphite negative electrode surface, also had to anode
Preferable oxidation stability, the effective working performance improved under electrolyte low temperature, extends longevity time of dynamic lithium battery entirety
Life (improves the storage service life of battery)；
6) additive e can be complexed with lithium ion, carry out ion transmission, so as to eliminate dynamic lithium battery electrolysis liquid
It is due to the acidic materials that lithium hexafluoro phosphate hydrolyzes and generates, to improve the performance of dynamic lithium battery.
Modified graphene, additive a, additive b, additive it can be seen from embodiment 3 and the data of comparative example 1-7
C, additive d, additive e addition simultaneously prepare dynamic lithium battery electrolysis liquid, using battery made of the above electrolyte, modified stone
Black alkene, additive a, additive b, additive c, additive d, additive e produce synergistic effect, significantly improve power lithium battery
The high and low temperature performance and cycle performance in pond.
The foregoing is only a preferred embodiment of the present invention, is not intended to restrict the invention, for the skill of this field
For art personnel, the invention may be variously modified and varied.All within the spirits and principles of the present invention, made any to repair
Change, equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.
Claims (6)
1. a kind of dynamic lithium battery of containing graphene, including electrode group and dynamic lithium battery are electrolysed liquid, the electrode group and power
Lithium battery electrolytes are sealed in battery case, and the electrode group includes the positive electrode, the negative electrode and the separator, which is characterized in that described dynamic
Power lithium battery electrolytes, as unit of parts by weight, including following raw material: 2-6 parts of lithium hexafluoro phosphate, 26-40 parts of methyl ethyl carbonate,
16-25 parts of dimethyl carbonate, 8-15 parts of butylene carbonate, 6-12 parts of dipropyl carbonate, 5-8 parts of Ethyl formate, propyl acetate 4-9
Part, 10-14 parts of 1,2- dimethoxy-ethane, 0.6-1 parts of modified graphene and a0.5-0.8 parts of additive；
The preparation method of the modified graphene, comprising the following steps: S1: by graphene magnetic field strength be 4800-7000GS,
Ultrasonic power is 220-580W, and temperature is 40-56 DEG C, and revolving speed is to stir 15-42min under 200-300r/min, and graphite is made
Alkene energy powder；
S2: being added neopelex into graphene energy powder made from step S1, is 52-75 DEG C in temperature, turns
Speed is modified 1-2h under 90-150r/min, and modified graphene is made；
The additive a is as unit of parts by weight, including following raw material: 4-10 parts of glycerin monostearate, 2-4 parts of sucrose ester,
1-2 parts and polysorbate 3-5 parts of Pluronic F68.
2. the dynamic lithium battery of containing graphene according to claim 1, which is characterized in that the dynamic lithium battery electrolysis
Liquid further includes following raw material as unit of parts by weight: b0.3-0.5 parts of additive, the additive b as unit of parts by weight,
Including following raw material: 7-15 parts and 2-6 parts of tetramethyl siloxanes of ethyleneglycol dimethyacrylate.
3. the dynamic lithium battery of containing graphene according to claim 2, which is characterized in that the dynamic lithium battery electrolysis
Liquid further includes following raw material as unit of parts by weight: c0.2-0.4 parts of additive, the additive c as unit of parts by weight,
Including following raw material: acrylate modified butadiene resin 12-20 parts and 4-12 parts of acrylic resin polyurethane copolymerization resin.
4. the dynamic lithium battery of containing graphene according to claim 3, which is characterized in that the dynamic lithium battery electrolysis
Liquid further includes following raw material as unit of parts by weight: d0.2-0.3 parts of additive, the additive d as unit of parts by weight,
Including following raw material: 8-12 parts of ethanedioic acid two (Butoxyethoxy second) ester, 4-10 parts of vinylene carbonate and 1,3-N-morpholinopropanesulfonic acid
5-9 parts of lactone.
5. the dynamic lithium battery of containing graphene according to claim 4, which is characterized in that the dynamic lithium battery electrolysis
Liquid further includes following raw material as unit of parts by weight: e0.3-0.6 parts of additive, the additive e is 1,3- diketone.
6. the dynamic lithium battery of containing graphene according to claim 5, which is characterized in that the dynamic lithium battery is electrolysed liquid
Preparation method, comprising the following steps:
(1) by methyl ethyl carbonate, dimethyl carbonate, butylene carbonate and 1 in closed environment, 2- dimethoxy-ethane is uniformly mixed
It closes；
(2) lithium hexafluoro phosphate, modified graphene, additive a, additive b and additive c is then added to be sufficiently mixed；
(3) dipropyl carbonate, Ethyl formate, propyl acetate, additive d and additive e are eventually adding to be uniformly mixed, power is made
Lithium battery electrolytes.
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| CN104370286A (en) * | 2014-11-04 | 2015-02-25 | 张泽宇 | Novel graphene preparation technique |
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