CN107482250A - A kind of dynamic lithium battery of graphene-containing - Google Patents
A kind of dynamic lithium battery of graphene-containing Download PDFInfo
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- CN107482250A CN107482250A CN201710534875.3A CN201710534875A CN107482250A CN 107482250 A CN107482250 A CN 107482250A CN 201710534875 A CN201710534875 A CN 201710534875A CN 107482250 A CN107482250 A CN 107482250A
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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 129
- 230000000996 additive effect Effects 0.000 claims abstract description 129
- 239000007788 liquid Substances 0.000 claims abstract description 54
- 239000002994 raw material Substances 0.000 claims abstract description 48
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 45
- 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
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 14
- 239000010452 phosphate Substances 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
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-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
- 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
- 230000004888 barrier function Effects 0.000 claims abstract description 9
- VUPKGFBOKBGHFZ-UHFFFAOYSA-N dipropyl carbonate Chemical compound CCCOC(=O)OCCC VUPKGFBOKBGHFZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000003792 electrolyte Substances 0.000 claims description 35
- -1 sucrose ester Chemical class 0.000 claims description 26
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 18
- 239000000843 powder Substances 0.000 claims description 12
- 238000002360 preparation method Methods 0.000 claims description 10
- 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
- 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
- 229910002804 graphite Inorganic materials 0.000 claims description 4
- 239000010439 graphite Substances 0.000 claims description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical group CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 4
- 239000004925 Acrylic resin Substances 0.000 claims description 3
- 229920000178 Acrylic resin Polymers 0.000 claims description 3
- HQPMKSGTIOYHJT-UHFFFAOYSA-N ethane-1,2-diol;propane-1,2-diol Chemical compound OCCO.CC(O)CO HQPMKSGTIOYHJT-UHFFFAOYSA-N 0.000 claims description 3
- 229920001993 poloxamer 188 Polymers 0.000 claims description 3
- 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
- 238000000034 method Methods 0.000 description 12
- 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
- 150000001875 compounds Chemical class 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 230000006399 behavior Effects 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 3
- 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
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification 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
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 230000008595 infiltration Effects 0.000 description 2
- 238000001764 infiltration 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
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- BQODPTQLXVVEJG-UHFFFAOYSA-N [O].C=C Chemical compound [O].C=C BQODPTQLXVVEJG-UHFFFAOYSA-N 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 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
- 238000011161 development Methods 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
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229920001983 poloxamer Polymers 0.000 description 1
- 238000006467 substitution reaction Methods 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
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- 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 battery of graphene-containing, including electrode group and dynamic lithium battery electrolysis liquid, the electrode group and dynamic lithium battery are electrolysed liquid-tight be enclosed in battery container, the electrode group includes positive pole, negative pole and barrier film, the dynamic lithium battery is electrolysed liquid, in units of parts by weight, including following raw material：26 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, 58 parts of Ethyl formate, 49 parts of propyl acetate, 10 14 parts of 1,2 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 of dynamic lithium battery and cycle performance 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 cell art, and in particular to a kind of dynamic lithium battery of graphene-containing.
【Background technology】
In recent years, with the rapid development of lithium electricity industry, lithium ion battery starts to enter electric car 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 electrokinetic cell, LiMn2O4 gradually plays
Go out its advantage, turn into one of positive electrode of main flow.Lithium-ion battery electrolytes occupy critically important position in lithium ion battery
Put, it directly affects the electrical property of lithium ion battery.The bath composition main electrolyte salt and solvent of lithium ion battery at present
Composition, wherein solvent are typically using carbonates mixed solvent such as ethylene carbonate EC, propylene carbonate ester PC, methyl ethyl carbonate
EMC, dimethyl carbonate DMC, diethyl carbonate DEC etc., conventional electrolytic salt are lithium hexafluoro phosphate LiPF6。
Lithium ion battery have the advantages that voltage platform it is high, it is without memory can, be widely applied.But lithium ion simultaneously
One of an important factor for application 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 is more to use LiPF6The electrolyte of/EC+DMC+EMC compositions, wherein
EC, DMC and EMC volume ratio 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, during especially for use in the lithium ion battery of LiMn2O4 system,
High temp effect performance is poor, can not meet the needs of dynamic lithium battery, be further improved.
【The content of the invention】
The technical problem to be solved in the present invention is to provide a kind of dynamic lithium battery of graphene-containing, to solve existing lithium ion
Battery uses LiPF6The electrolyte of/EC+DMC+EMC compositions, low and high temperature cycle performance is not ideal enough, and high temp effect performance is compared
Difference, the problems such as can not meeting the needs of dynamic lithium battery.
In order to solve the above technical problems, the present invention uses following technical scheme：
A kind of dynamic lithium battery of graphene-containing, including electrode group and dynamic lithium battery electrolysis liquid, the electrode group and dynamic
Power lithium battery electrolytes are sealed in battery container, and the electrode group includes positive pole, negative pole and barrier film, the power lithium cell electric
Liquid is solved, in units of parts by weight, including following raw material：Lithium hexafluoro phosphate 2-6 parts, methyl ethyl carbonate 26-40 parts, dimethyl carbonate
16-25 parts, butylene carbonate 8-15 parts, dipropyl carbonate 6-12 parts, Ethyl formate 5-8 parts, propyl acetate 4-9 parts, 1,2- bis-
Ethyl Methyl Ether 10-14 parts, modified graphene 0.6-1 parts, additive a 0.5-0.8 parts；
The preparation method of the modified graphene, comprises the following steps：S1：In magnetic field intensity it is 4800- by graphene
7000GS, ultrasonic power 220-580W, temperature are 40-56 DEG C, and rotating speed is under 200-300r/min, stirs 15-42min,
Graphene energy powder is made；
S2：Neopelex is added into graphene energy powder made from step S1, is 52-75 in temperature
DEG C, rotating speed is modified 1-2h under 90-150r/min, and modified graphene is made；
The additive a is in units of parts by weight, including following raw material：Glycerin monostearate 4-10 parts, sucrose ester 2-4
Part, Pluronic F68 1-2 parts, polysorbate 3-5 parts.
Further, the dynamic lithium battery electrolysis liquid, in units of parts by weight, in addition to following raw material：Additive b
0.3-0.5 parts, the additive b is in units of parts by weight, including following raw material：Ethyleneglycol dimethyacrylate 7-15 parts,
Tetramethyl siloxanes 2-6 parts.
Further, the dynamic lithium battery electrolysis liquid, in units of parts by weight, in addition to following raw material：Additive c
0.2-0.4 parts, the additive c is in units of parts by weight, including following raw material：Acrylate modified butadiene resin 12-20
Part, acrylic resin polyurethane copolymerization resin 4-12 parts.
Further, the dynamic lithium battery electrolysis liquid, in units of parts by weight, in addition to following raw material：Additive d
0.2-0.3 parts, the additive d is in units of parts by weight, including following raw material：Ethanedioic acid two (Butoxyethoxy second) ester 8-
12 parts, vinylene carbonate 4-10 parts, PS 5-9 parts.
Further, the dynamic lithium battery electrolysis liquid, in units of parts by weight, in addition to following raw material：Additive e
0.3-0.6 parts, the additive e are 1,3- diketone.
Further, the preparation method of the dynamic lithium battery electrolysis liquid, comprises the following steps：
(1) it is in closed environment that methyl ethyl carbonate, dimethyl carbonate, butylene carbonate, 1,2- dimethoxy-ethanes is equal
Even mixing；
(2) and then addition lithium hexafluoro phosphate, modified graphene, additive a, additive b, additive c are sufficiently mixed；
(3) sour dipropyl, Ethyl formate, propyl acetate, additive d, additive e are eventually adding to be well mixed, is made dynamic
Power lithium battery electrolytes.
The invention has the advantages that：
(1) modified graphene, additive a, additive b, additive c, additive d, additive e effect difference are as follows：
1) graphene becomes hydrophobicity by modification, be advantageous to it is compatible with organic solvent, so as 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
The absorption infiltration of pole piece and barrier film to electrolyte, makes electrolyte be rapidly achieved the state of stable and uniform in the battery, can improve
The cycle life of dynamic lithium battery.
3) additive b forms layer protecting film during initial charge in positive electrode surface, reduces electrolyte in positive pole table
Aerogenesis is decomposed in face, and in subsequent charge and discharge process, can suppress the Mn in positive active material2+The dissolving of ion,
Improve the high-temperature behavior of lithium manganate battery.
4) additive c can make negative terminal surface form layer protecting film；
5) additive d can improve the electrolyte cryogenic property of dynamic lithium battery, from (the Butoxyethoxy of ethanedioic acid two
Second) ester, vinylene carbonate, PS add as the preparing raw material that can reduce temperature additive d, electrolyte
The decomposition voltage of electrolyte can be effectively improved after agent d by adding, and can form passivating film on composite graphite negative electrode surface, also have to positive pole
Preferable oxidation stability, the effective service behaviour improved under electrolyte low temperature, extend dynamic lithium battery overall longevity time
Life (the storage service life for improving battery)；
6) additive e can be complexed with lithium ion, carry out ion transmission, so as to eliminate dynamic lithium battery electrolysis liquid
System's caused acidic materials due to lithium hexafluoro phosphate hydrolysis, so as to improve the performance of dynamic lithium battery.
Modified graphene, additive a, additive b, additive it can be seen from embodiment 3 and comparative example 1-7 data
C, additive d, additive e addition simultaneously prepare dynamic lithium battery electrolysis liquid, using battery made of above electrolyte, modified stone
Black alkene, additive a, additive b, additive c, additive d, additive e generate synergy, 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.
【Embodiment】
For ease of more fully understanding the present invention, it is illustrated by following instance, these examples belong to the protection of the present invention
Scope, but do not limit the scope of the invention.
In embodiment, the dynamic lithium battery, including electrode group and dynamic lithium battery electrolysis liquid, the electrode group and dynamic
Power lithium battery electrolytes are sealed in battery container, and the electrode group includes positive pole, negative pole and barrier film, the power lithium cell electric
Liquid is solved, in units of parts by weight, including following raw material：Lithium hexafluoro phosphate 2-6 parts, methyl ethyl carbonate 26-40 parts, dimethyl carbonate
16-25 parts, butylene carbonate 8-15 parts, dipropyl carbonate 6-12 parts, Ethyl formate 5-8 parts, propyl acetate 4-9 parts, 1,2- bis-
Ethyl Methyl Ether 10-14 parts, modified graphene 0.6-1 parts, additive a 0.5-0.8 parts, additive b 0.3-0.5 parts, addition
Agent c 0.2-0.4 parts, additive d 0.2-0.3 parts, additive e 0.3-0.6 parts；
The preparation method of the modified graphene, comprises the following steps：S1：In magnetic field intensity it is 4800- by graphene
7000GS, ultrasonic power 220-580W, temperature are 40-56 DEG C, and rotating speed is under 200-300r/min, stirs 15-42min,
Graphene energy powder is made；
S2：Neopelex is added into graphene energy powder made from step S1, is 52-75 in temperature
DEG C, rotating speed is modified 1-2h under 90-150r/min, and modified graphene is made；
The additive a is in units of parts by weight, including following raw material：Glycerin monostearate 4-10 parts, sucrose ester 2-4
Part, Pluronic F68 1-2 parts, polysorbate 3-5 parts；
The additive b is in units of parts by weight, including following raw material：Ethyleneglycol dimethyacrylate 7-15 parts, four
Methylsiloxane 2-6 parts；
The additive c is in units of parts by weight, including following raw material：Acrylate modified butadiene resin 12-20 parts,
Acrylic resin polyurethane copolymerization resin 4-12 parts；
The additive d is in units of parts by weight, including following raw material：Ethanedioic acid two (Butoxyethoxy second) ester 8-12
Part, vinylene carbonate 4-10 parts, PS 5-9 parts；
The additive e is 1,3- diketone.
The preparation method of the dynamic lithium battery electrolysis liquid, comprises the following steps：
(1) it is in closed environment that methyl ethyl carbonate, dimethyl carbonate, butylene carbonate, 1,2- dimethoxy-ethanes is equal
Even mixing；
(2) and then addition lithium hexafluoro phosphate, modified graphene, additive a, additive b, additive c are sufficiently mixed；
(3) sour dipropyl, Ethyl formate, propyl acetate, additive d, additive e are eventually adding to be well mixed, is made dynamic
Power lithium battery electrolytes.
Below by more specific embodiment, the present invention will be described.
Embodiment 1
A kind of dynamic lithium battery of graphene-containing, including electrode group and dynamic lithium battery electrolysis liquid, the electrode group and dynamic
Power lithium battery electrolytes are sealed in battery container, and the electrode group includes positive pole, negative pole and barrier film, the power lithium cell electric
Liquid is solved, in units 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, 10 parts of dipropyl carbonate, 7 parts of Ethyl formate, 6 parts of propyl acetate, 12 parts of 1,2- dimethoxy-ethanes, change
0.8 part of graphene of property, 0.7 part of additive a, 0.4 part of additive b, 0.3 part of additive c, 0.2 part of additive d, additive e
0.5 part；
The preparation method of the modified graphene, comprises the following steps：S1：In magnetic field intensity it is 6000GS by graphene,
Ultrasonic power is 400W, and temperature is 50 DEG C, and rotating speed is under 200r/min, stirs 30min, and graphene energy powder is made；
S2：Neopelex is added 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 in units of parts by weight, including following raw material：7 parts of glycerin monostearate, 3 parts of sucrose ester, gather
Oxygen ethene-poiyoxypropylene copolymer 1.6-2 parts, 4 parts of polysorbate；
The additive b is in units of parts by weight, including following raw material：12 parts of ethyleneglycol dimethyacrylate, tetramethyl
4 parts of radical siloxane；
The additive c is in units of parts by weight, including following raw material：Acrylate modified 16 parts of butadiene resin, third
8 parts of olefin(e) acid resin polyurethane copolymerization resin；
The additive d is in units of parts by weight, including following raw material：Ethanedioic acid two (Butoxyethoxy second) ester 10
Part, 8 parts of vinylene carbonate, 7 parts of PS；
The additive e is 1,3- diketone.
The preparation method of the dynamic lithium battery electrolysis liquid, comprises the following steps：
(1) it is in closed environment that methyl ethyl carbonate, dimethyl carbonate, butylene carbonate, 1,2- dimethoxy-ethanes is equal
Even mixing；
(2) and then addition lithium hexafluoro phosphate, modified graphene, additive a, additive b, additive c are sufficiently mixed；
(3) sour dipropyl, Ethyl formate, propyl acetate, additive d, additive e are eventually adding to be well mixed, is made dynamic
Power lithium battery electrolytes.
1665132 batteries of 20 non-fluid injections are randomly selected, this 20 pieces of batteries are injected separately into this in constant temperature and humidity room
The dynamic lithium battery electrolysis liquid that embodiment provides, according to a conventional method by the battery of fluid injection carry out aging, chemical conversion, degasification, sealing,
Partial volume, dynamic lithium battery is made.
Embodiment 2
A kind of dynamic lithium battery of graphene-containing, including electrode group and dynamic lithium battery electrolysis liquid, the electrode group and dynamic
Power lithium battery electrolytes are sealed in battery container, and the electrode group includes positive pole, negative pole and barrier film, the power lithium cell electric
Liquid is solved, in units 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-ethanes,
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, addition
0.3 part of agent e；
The preparation method of the modified graphene, comprises the following steps：S1：In magnetic field intensity it is 4800GS by graphene,
Ultrasonic power is 220W, and temperature is 40 DEG C, and rotating speed is under 200r/min, stirs 42min, and graphene energy powder is made；
S2：Neopelex is added 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 in units of parts by weight, including following raw material：4 parts of glycerin monostearate, 2 parts of sucrose ester, gather
Oxygen ethene -1 part of poiyoxypropylene copolymer, 3 parts of polysorbate；
The additive b is in units of parts by weight, including following raw material：7 parts of ethyleneglycol dimethyacrylate, tetramethyl
2 parts of siloxanes；
The additive c is in units of parts by weight, including following raw material：Acrylate modified 12 parts of butadiene resin, third
4 parts of olefin(e) acid resin polyurethane copolymerization resin；
The additive d is in units of parts by weight, including following raw material：8 parts of ethanedioic acid two (Butoxyethoxy second) ester,
4 parts of vinylene carbonate, 5 parts of PS；
The additive e is 1,3- diketone.
The compound method for the dynamic lithium battery electrolysis liquid that the present embodiment provides is the same as embodiment 1.
1665132 batteries of 20 non-fluid injections are randomly selected, this 20 pieces of batteries are injected separately into this in constant temperature and humidity room
The dynamic lithium battery electrolysis liquid that embodiment provides, according to a conventional method by the battery of fluid injection carry out aging, chemical conversion, degasification, sealing,
Partial volume, dynamic lithium battery is made.
Embodiment 3
A kind of dynamic lithium battery of graphene-containing, including electrode group and dynamic lithium battery electrolysis liquid, the electrode group and dynamic
Power lithium battery electrolytes are sealed in battery container, and the electrode group includes positive pole, negative pole and barrier film, the power lithium cell electric
Liquid is solved, in units 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-ethanes 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, add
Add 0.6 part of agent e；
The preparation method of the modified graphene, comprises the following steps：S1：In magnetic field intensity it is 7000GS by graphene,
Ultrasonic power is 580W, and temperature is 56 DEG C, and rotating speed is under 300r/min, stirs 15min, and graphene energy powder is made；
S2：Neopelex is added 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 in units of parts by weight, including following raw material：10 parts of glycerin monostearate, 4 parts of sucrose ester,
2 parts of Pluronic F68,5 parts of polysorbate；
The additive b is in units of parts by weight, including following raw material：15 parts of ethyleneglycol dimethyacrylate, tetramethyl
6 parts of radical siloxane；
The additive c is in units of parts by weight, including following raw material：Acrylate modified 20 parts of butadiene resin, third
12 parts of olefin(e) acid resin polyurethane copolymerization resin；
The additive d is in units of parts by weight, including following raw material：Ethanedioic acid two (Butoxyethoxy second) ester 12
Part, 10 parts of vinylene carbonate, 9 parts of PS；
The additive e is 1,3- diketone.
The compound method for the dynamic lithium battery electrolysis liquid that the present embodiment provides is the same as embodiment 1.
1665132 batteries of 20 non-fluid injections are randomly selected, this 20 pieces of batteries are injected separately into this in constant temperature and humidity room
The dynamic lithium battery electrolysis liquid that embodiment provides, according to a conventional method by the battery of fluid injection carry out aging, chemical conversion, degasification, sealing,
Partial volume, dynamic lithium battery is made.
Comparative example 1
Compared with Example 3, unlike having only：Prepare and lack modified graphene, addition in the raw material of dynamic lithium battery
Agent a, additive b, additive c, additive d, additive e.
The compound method for the dynamic lithium battery electrolysis liquid that this comparative example provides is the same as embodiment 3.
1665132 batteries of 20 non-fluid injections are randomly selected, this 20 pieces of batteries are injected separately into this in constant temperature and humidity room
The dynamic lithium battery electrolysis liquid that comparative example provides, according to a conventional method by the battery of fluid injection carry out aging, chemical conversion, degasification, sealing,
Partial volume, dynamic lithium battery is made.
Comparative example 2
Compared with Example 3, unlike having only：Prepare in the raw material of dynamic lithium battery and lack modified graphene.
The compound method for the dynamic lithium battery electrolysis liquid that this comparative example provides is the same as embodiment 3.
1665132 batteries of 20 non-fluid injections are randomly selected, this 20 pieces of batteries are injected separately into this in constant temperature and humidity room
The dynamic lithium battery electrolysis liquid that comparative example provides, according to a conventional method by the battery of fluid injection carry out aging, chemical conversion, degasification, sealing,
Partial volume, dynamic lithium battery is made.
Comparative example 3
Compared with Example 3, unlike having only：Prepare and lack additive a in the raw material of dynamic lithium battery.
The compound method for the dynamic lithium battery electrolysis liquid that this comparative example provides is the same as embodiment 3.
1665132 batteries of 20 non-fluid injections are randomly selected, this 20 pieces of batteries are injected separately into this in constant temperature and humidity room
The dynamic lithium battery electrolysis liquid that comparative example provides, according to a conventional method by the battery of fluid injection carry out aging, chemical conversion, degasification, sealing,
Partial volume, dynamic lithium battery is made.
Comparative example 4
Compared with Example 3, unlike having only：Prepare and lack additive b in the raw material of dynamic lithium battery.
The compound method for the dynamic lithium battery electrolysis liquid that this comparative example provides is the same as embodiment 3.
1665132 batteries of 20 non-fluid injections are randomly selected, this 20 pieces of batteries are injected separately into this in constant temperature and humidity room
The dynamic lithium battery electrolysis liquid that comparative example provides, according to a conventional method by the battery of fluid injection carry out aging, chemical conversion, degasification, sealing,
Partial volume, dynamic lithium battery is made.
Comparative example 5
Compared with Example 3, unlike having only：Prepare and lack additive c in the raw material of dynamic lithium battery.
The compound method for the dynamic lithium battery electrolysis liquid that this comparative example provides is the same as embodiment 3.
1665132 batteries of 20 non-fluid injections are randomly selected, this 20 pieces of batteries are injected separately into this in constant temperature and humidity room
The dynamic lithium battery electrolysis liquid that comparative example provides, according to a conventional method by the battery of fluid injection carry out aging, chemical conversion, degasification, sealing,
Partial volume, dynamic lithium battery is made.
Comparative example 6
Compared with Example 3, unlike having only：Prepare and lack additive d in the raw material of dynamic lithium battery.
The compound method for the dynamic lithium battery electrolysis liquid that this comparative example provides is the same as embodiment 3.
1665132 batteries of 20 non-fluid injections are randomly selected, this 20 pieces of batteries are injected separately into this in constant temperature and humidity room
The dynamic lithium battery electrolysis liquid that comparative example provides, according to a conventional method by the battery of fluid injection carry out aging, chemical conversion, degasification, sealing,
Partial volume, dynamic lithium battery is made.
Comparative example 7
Compared with Example 3, unlike having only：Prepare and lack additive e in the raw material of dynamic lithium battery.
The compound method for the dynamic lithium battery electrolysis liquid that this comparative example provides is the same as embodiment 3.
1665132 batteries of 20 non-fluid injections are randomly selected, this 20 pieces of batteries are injected separately into this in constant temperature and humidity room
The dynamic lithium battery electrolysis liquid that comparative example provides, according to a conventional method by the battery of fluid injection carry out aging, chemical conversion, degasification, sealing,
Partial volume, dynamic lithium battery is made.
For ease of 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), the described same a collection of preamble production technology for referring to 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, negative pole 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 discharges respectively, -20 DEG C,
1C discharges, -35 DEG C, 0.2C electric discharges, normal temperature (25 DEG C) 1C loop tests, 55 DEG C of high temperature, 1C loop tests, test result such as following table
It is shown.
As seen from the above table：(1) be can be seen that by the test result of upper table using power lithium cell electric provided by the invention
It is excellent to solve the high and low temperature performance of dynamic lithium battery and cycle performance made from liquid, dynamic lithium battery electrolysis liquid provided by the invention
It is worthy of popularization.
(2) modified graphene, additive a, additive b, additive c, additive d, additive e effect difference are as follows：
1) graphene becomes hydrophobicity by modification, be advantageous to it is compatible with organic solvent, so as 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
The absorption infiltration of pole piece and barrier film to electrolyte, makes electrolyte be rapidly achieved the state of stable and uniform in the battery, can improve
The cycle life of dynamic lithium battery.
3) additive b forms layer protecting film during initial charge in positive electrode surface, reduces electrolyte in positive pole table
Aerogenesis is decomposed in face, and in subsequent charge and discharge process, can suppress the Mn in positive active material2+The dissolving of ion,
Improve the high-temperature behavior of lithium manganate battery.
4) additive c can make negative terminal surface form layer protecting film；
5) additive d can improve the electrolyte cryogenic property of dynamic lithium battery, from (the Butoxyethoxy of ethanedioic acid two
Second) ester, vinylene carbonate, PS add as the preparing raw material that can reduce temperature additive d, electrolyte
The decomposition voltage of electrolyte can be effectively improved after agent d by adding, and can form passivating film on composite graphite negative electrode surface, also have to positive pole
Preferable oxidation stability, the effective service behaviour improved under electrolyte low temperature, extend dynamic lithium battery overall longevity time
Life (the storage service life for improving battery)；
6) additive e can be complexed with lithium ion, carry out ion transmission, so as to eliminate dynamic lithium battery electrolysis liquid
System's caused acidic materials due to lithium hexafluoro phosphate hydrolysis, so as to improve the performance of dynamic lithium battery.
Modified graphene, additive a, additive b, additive it can be seen from embodiment 3 and comparative example 1-7 data
C, additive d, additive e addition simultaneously prepare dynamic lithium battery electrolysis liquid, using battery made of above electrolyte, modified stone
Black alkene, additive a, additive b, additive c, additive d, additive e generate synergy, significantly improve power lithium battery
The high and low temperature performance and cycle performance in pond.
The preferred embodiments of the present invention are the foregoing is only, are not intended to limit the invention, for the skill of this area
For art personnel, the present invention can have various modifications and variations.Within the spirit and principles of the invention, that is made any repaiies
Change, equivalent substitution, improvement etc., should be included in the scope of the protection.
Claims (6)
1. a kind of dynamic lithium battery of graphene-containing, including electrode group and dynamic lithium battery electrolysis liquid, the electrode group and power
Lithium battery electrolytes are sealed in battery container, and the electrode group includes positive pole, negative pole and barrier film, it is characterised in that described dynamic
Power lithium battery electrolytes, in units of parts by weight, including following raw material：Lithium hexafluoro phosphate 2-6 parts, methyl ethyl carbonate 26-40 parts,
Dimethyl carbonate 16-25 parts, butylene carbonate 8-15 parts, dipropyl carbonate 6-12 parts, Ethyl formate 5-8 parts, propyl acetate 4-9
Part, 1,2- dimethoxy-ethane 10-14 parts, modified graphene 0.6-1 parts, additive a 0.5-0.8 parts；
The preparation method of the modified graphene, comprises the following steps：S1：In magnetic field intensity it is 4800-7000GS by graphene,
Ultrasonic power is 220-580W, and temperature is 40-56 DEG C, and rotating speed is under 200-300r/min, stirs 15-42min, and graphite is made
Alkene energy powder；
S2：Neopelex is added 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 in units of parts by weight, including following raw material：Glycerin monostearate 4-10 parts, sucrose ester 2-4 parts,
Pluronic F68 1-2 parts, polysorbate 3-5 parts.
2. the dynamic lithium battery of graphene-containing according to claim 1, it is characterised in that the dynamic lithium battery electrolysis
Liquid, in units of parts by weight, in addition to following raw material：Additive b 0.3-0.5 parts, the additive b in units of parts by weight,
Including following raw material：Ethyleneglycol dimethyacrylate 7-15 parts, tetramethyl siloxanes 2-6 parts.
3. the dynamic lithium battery of graphene-containing according to claim 2, it is characterised in that the dynamic lithium battery electrolysis
Liquid, in units of parts by weight, in addition to following raw material：Additive c 0.2-0.4 parts, the additive c in units of parts by weight,
Including following raw material：Acrylate modified butadiene resin 12-20 parts, acrylic resin polyurethane copolymerization resin 4-12 parts.
4. the dynamic lithium battery of graphene-containing according to claim 3, it is characterised in that the dynamic lithium battery electrolysis
Liquid, in units of parts by weight, in addition to following raw material：Additive d 0.2-0.3 parts, the additive d in units of parts by weight,
Including following raw material：(Butoxyethoxy second) the ester 8-12 of ethanedioic acid two parts, vinylene carbonate 4-10 parts, 1, in 3-N-morpholinopropanesulfonic acid
Ester 5-9 parts.
5. the dynamic lithium battery of graphene-containing according to claim 4, it is characterised in that the dynamic lithium battery electrolysis
Liquid, in units of parts by weight, in addition to following raw material：Additive e 0.3-0.6 parts, the additive e are 1,3- diketone.
6. the dynamic lithium battery of graphene-containing according to claim 5, it is characterised in that the dynamic lithium battery is electrolysed liquid
Preparation method, comprise the following steps：
(1) methyl ethyl carbonate, dimethyl carbonate, butylene carbonate, 1,2- dimethoxy-ethanes are uniformly mixed in closed environment
Close；
(2) and then addition lithium hexafluoro phosphate, modified graphene, additive a, additive b, additive c are sufficiently mixed；
(3) sour dipropyl, Ethyl formate, propyl acetate, additive d, additive e are eventually adding to be well mixed, power lithium is made
Battery electrolyte.
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