CN102683745B - Voltage is the preparation method of the electrolyte of the new type lithium ion battery of 5V - Google Patents
Voltage is the preparation method of the electrolyte of the new type lithium ion battery of 5V Download PDFInfo
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- CN102683745B CN102683745B CN201210055980.6A CN201210055980A CN102683745B CN 102683745 B CN102683745 B CN 102683745B CN 201210055980 A CN201210055980 A CN 201210055980A CN 102683745 B CN102683745 B CN 102683745B
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- electrolyte
- additive
- voltage
- lithium ion
- ion battery
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 51
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000000654 additive Substances 0.000 claims abstract description 27
- 230000000996 additive effect Effects 0.000 claims abstract description 27
- 239000012046 mixed solvent Substances 0.000 claims abstract description 16
- WXBWKMLIVXELSF-UHFFFAOYSA-N 2,2,2-trifluoro-n,n-dimethylacetamide Chemical group CN(C)C(=O)C(F)(F)F WXBWKMLIVXELSF-UHFFFAOYSA-N 0.000 claims abstract description 8
- 150000002148 esters Chemical class 0.000 claims abstract description 8
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 8
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims description 12
- LAVARTIQQDZFNT-UHFFFAOYSA-N 1-(1-methoxypropan-2-yloxy)propan-2-yl acetate Chemical compound COCC(C)OCC(C)OC(C)=O LAVARTIQQDZFNT-UHFFFAOYSA-N 0.000 claims description 9
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 7
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 5
- ACFSQHQYDZIPRL-UHFFFAOYSA-N lithium;bis(1,1,2,2,2-pentafluoroethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)C(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)C(F)(F)F ACFSQHQYDZIPRL-UHFFFAOYSA-N 0.000 claims description 3
- BUHVIAUBTBOHAG-FOYDDCNASA-N (2r,3r,4s,5r)-2-[6-[[2-(3,5-dimethoxyphenyl)-2-(2-methylphenyl)ethyl]amino]purin-9-yl]-5-(hydroxymethyl)oxolane-3,4-diol Chemical compound COC1=CC(OC)=CC(C(CNC=2C=3N=CN(C=3N=CN=2)[C@H]2[C@@H]([C@H](O)[C@@H](CO)O2)O)C=2C(=CC=CC=2)C)=C1 BUHVIAUBTBOHAG-FOYDDCNASA-N 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 7
- 150000001298 alcohols Chemical class 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 6
- 239000010405 anode material Substances 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000000354 decomposition reaction Methods 0.000 abstract description 2
- 229910002096 lithium permanganate Inorganic materials 0.000 description 7
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 6
- 150000005676 cyclic carbonates Chemical class 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910011279 LiCoPO4 Inorganic materials 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- CUDYYMUUJHLCGZ-UHFFFAOYSA-N 2-(2-methoxypropoxy)propan-1-ol Chemical compound COC(C)COC(C)CO CUDYYMUUJHLCGZ-UHFFFAOYSA-N 0.000 description 2
- -1 Carboxylic acid esters sulfite Chemical class 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 239000005030 aluminium foil Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 239000011268 mixed slurry Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- PZTAGFCBNDBBFZ-UHFFFAOYSA-N tert-butyl 2-(hydroxymethyl)piperidine-1-carboxylate Chemical compound CC(C)(C)OC(=O)N1CCCCC1CO PZTAGFCBNDBBFZ-UHFFFAOYSA-N 0.000 description 2
- CUVLMZNMSPJDON-UHFFFAOYSA-N 1-(1-butoxypropan-2-yloxy)propan-2-ol Chemical compound CCCCOCC(C)OCC(C)O CUVLMZNMSPJDON-UHFFFAOYSA-N 0.000 description 1
- IDQBJILTOGBZCR-UHFFFAOYSA-N 1-butoxypropan-1-ol Chemical compound CCCCOC(O)CC IDQBJILTOGBZCR-UHFFFAOYSA-N 0.000 description 1
- 229910013385 LiN(SO2C2F5)2 Inorganic materials 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 241000519996 Teucrium chamaedrys Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
Classifications
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- 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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Abstract
The present invention relates to the preparation method that a kind of voltage is the electrolyte of the new type lithium ion battery of 5V, step is as follows: 1) by alcohols material and Ester respectively purifying dewater after mixing, obtain mixed solvent; 2) lithium salts is dissolved in above-mentioned mixed solvent, obtains not containing the electrolyte of additive; 3) be dissolved in by additive above-mentioned not containing in the electrolyte of additive, described additive is N, N-dimethyl trifluoroacetamide (DTA), and obtaining is the electrolyte of 5V lithium ion battery for voltage.Advantage of the present invention is: this electrolyte can improve the compatibility of electrolyte and high-voltage anode, reduce the decomposition of electrolyte on high-voltage anode material surface in charging process, and stable SEI film can be formed on both positive and negative polarity surface, the charge/discharge capacity of positive electrode and cyclical stability are significantly improved; And technique is simple, easy to implement, raw material and cost of manufacture cheap, be suitable for suitability for industrialized production, have a extensive future.
Description
Technical field
The invention belongs to technical field of lithium ion, be specifically related to the preparation method that a kind of voltage is the electrolyte of the new type lithium ion battery of 5V
Background technology
In recent years, rechargeable lithium ion batteries system has become the important technology of global Battery Market.Up to the present, these batteries are batteries that in rechargeable battery, energy density is the highest.Although the lithium ion battery overwhelming majority of producing at present is only used to drive some midget plants as cell phone, notebook computer and moving photoconductor equipment, but the whole world is all in the progress of effort Push Technology, need to produce the higher new type lithium ion battery of voltage, more such as the requirement of answering of the large-scale quick charging battery of electric automobile to meet.
Alcohols material has higher flash-point usually even without flash-point, therefore uses alcohols material to be conducive to improving the security performance of battery being heated, under the state such as overcharge.There are good discharge capacity and cycle life.
N, N-dimethyl trifluoroacetamide (DTA). it is according to having viscosity low (1.09mpa.s, 25 DEG C), boiling point (135 DEG C) and flash-point (72 DEG C) high.Have good film forming ability also to have good oxidation stability to positive pole at graphite surface, can make the additive of electrolyte, the battery be assembled into has excellent cycle performance at low temperatures.
Summary of the invention
The object of the invention is the above-mentioned deficiency overcome existing for prior art, and to provide a kind of be the preparation method of the electrolyte of 5V lithium ion battery for voltage, the method technique is simple, easy to implement, low raw-material cost, be suitable for industrialization dirt produce, have a extensive future.
Its technical scheme is:
Voltage is a preparation method for the electrolyte of the new type lithium ion battery of 5V, and concrete steps are as follows:
1) by alcohols material and carbonic ester respectively purifying dewater after mixing, obtain mixed solvent;
2) lithium salts is dissolved in above-mentioned mixed solvent, obtains not containing the electrolyte of additive;
3) additive is dissolved in above-mentioned not containing in the electrolyte of additive, described additive is N, N-dimethyl trifluoroacetamide (DTA), obtains the electrolyte of the new type lithium ion battery for voltage being 5V.
Further preferably, it is characterized in that, step 1) in alcohols material have one or more ratios in dipropylene glycol methyl ether acetate (DPMA) and dipropylene glycol dibenzoate (DPGDB), 1-Methoxy-2-propyl acetate (PMA), dipropylene (DPNB), propandiol butyl ether (PNB), dipropylene glycol methyl ether (DPM) to mix arbitrarily.
Further preferably, step 1) described in Ester have cyclic carbonate; Linear carbonate; Carboxylic acid esters sulfite; The organic solvent of electrolyte is made up of cyclic carbonate and linear carbonate, can mix arbitrarily in cyclic carbonate and linear carbonate by one or more ratios.
Further preferably, step 1) described in Ester have cyclic carbonate (PC, EC); Linear carbonate (DEC, DMC, EMC); Carboxylic acid esters (MF, EF, EA, MA, MP, EP) sulfite (ES, DES, DMS); EC, PC etc. are mainly used to dissolve lithium salts, but viscosity is large, and the low viscosity solvents such as DMC, EMC are used for reducing mixed solvent viscosity, improve lithium ion conductivity; The organic solvent of electrolyte is generally made up of cyclic carbonate and linear carbonate.Can mix arbitrarily by one or more ratios in cyclic carbonate and linear carbonate.
Further preferably, step 2) described in lithium salts LiN (SO
2c
2f
5)
2(LiBETI) be 1MOL/1L in the concentration of alcohols material and carbonic ester.
Preferably further, step 3) the micro-performance just greatly can improving electrolyte of middle additive, described additive is N, N-dimethyl trifluoroacetamide (DTA). the consumption of additive is 3-3.5% with the mass ratio of the electrolyte not containing additive.
Beneficial effect of the present invention:
Compared with prior art, technical scheme of the present invention can improve the compatibility of electrolyte and high-voltage anode, reduce the decomposition of electrolyte on high-voltage anode material surface in charging process, and stable SEI film can be formed on both positive and negative polarity surface, the charge/discharge capacity of positive electrode and cyclical stability are significantly improved; And technique is simple, easy to implement, low raw-material cost, be suitable for suitability for industrialized production, has a extensive future.
Accompanying drawing explanation
Fig. 1 is the charge and discharge circulation life figure of LiMnO4 positive electrode in different electrolytes;
Fig. 2 is the charge and discharge circulation life figure of LiMnO4 positive electrode in different electrolytes.
Embodiment
Below in conjunction with concrete and embodiment, method of the present invention is described in more detail.
Voltage is a preparation method for the electrolyte of the new type lithium ion battery of 5V, and step is as follows
1) by ethylene carbonate (EC), methyl ethyl carbonate (EMC) and (DEC) purifying and mixing after dewatering respectively, mass ratio is 1: 1: 1, stir, by above-mentioned carbonic ester mixed solvent and dipropylene glycol methyl ether acetate (DPMA) mixing.Mass ratio is 1: 1, stirs and obtains mixed solvent.
2) acid imide lithium salts is dissolved in above-mentioned mixed solvent, is 1MOL/1L in the concentration of mixed solvent, stirs, obtain not containing the electrolyte of additive;
3) adding additive is N, N-dimethyl trifluoroacetamide (DTA), and its percentage consumption is 3% of electrolyte quality, makes it to dissolve, and stirs, and obtaining is the electrolyte of 5V lithium ion battery for voltage.
Effect detects
Take LiMnO4 as positive electrode, positive pole batching is according to active material: acetylene black: binding agent=76: the weight of 20: 10 carries out mixed slurry, and compressing tablet is dried.Adopt lithium metal as negative pole, aluminium foil and Copper Foil are respectively as both positive and negative polarity collector.
Adopt three kinds of different electrolyte in contrast test: A-be not containing the electrolyte of dipropylene glycol methyl ether acetate and N, N-dimethyl trifluoroacetamide (DTA), B-be do not contain the electrolyte of additive, C is that the present invention obtains is the Novel lithium-ion battery electrolyte of 5V for voltage.
Fig. 1 is the charge and discharge circulation life figure of LiMnO4 positive electrode in different electrolytes.Charging voltage is 3.2-5.1V, and charging and discharging currents is the display of 0.1C testing result: adopt respectively electrolyte A, B, C, time, be respectively 89 with LiCoPO4 positive electrode initial discharge specific capacity, 105.7,125.8mAh/g; Charge and discharge cycles is after 30 weeks, specific discharge capacity is respectively 27.8,39.7,76.8mAh/g, its capability retention is respectively 31.2,37.5,61%, after the electrolyte adopted containing additive is described, lithium ion anode material obtains discharge capacity under high voltages and charge-discharge performance obtains larger raising.
Embodiment 2
Voltage is a preparation method for the electrolyte of the new type lithium ion battery of 5V, and step is as follows
1) by ethylene carbonate (EC), methyl ethyl carbonate (DMC) and (DEC) purifying and mixing after dewatering respectively, mass ratio is 1: 2: 2, stir, by above-mentioned carbonic ester mixed solvent and dipropylene glycol methyl ether acetate (DPMA).Mass ratio is 1: 1, stirs and obtains mixed solvent.
2) lithium salts (LiBETI) is dissolved in above-mentioned mixing mAh/g solvent, is 1MOL/1L in the concentration of mixed solvent, stirs, obtain not containing the electrolyte of additive;
3) adding additive is N, N-dimethyl trifluoroacetamide (DTA), and its percentage consumption is 3.5% of electrolyte quality, makes it to dissolve, and stirs, and obtaining is the electrolyte of 5V lithium ion battery for voltage.
Effect detects
Take LiMnO4 as positive electrode, positive pole batching is according to active material: acetylene black: binding agent=76: the weight of 20: 10 carries out mixed slurry, and compressing tablet is dried.Adopt lithium metal as negative pole, aluminium foil and Copper Foil are respectively as both positive and negative polarity collector.
The electrolyte that three kinds different is adopted: A-is not containing dipropylene glycol methyl ether acetate and N in contrast test, the electrolyte of N-dimethyl trifluoroacetyl mAh/g amine (DTA), what B-was that the present invention obtains is the Novel lithium-ion battery electrolyte of 5V for voltage.
Fig. 2 is the charge and discharge circulation life figure of LiMnO4 positive electrode in different electrolytes.Charging voltage is 3.2-5.1V, charging and discharging currents is 0.1C. under the condition of electrolyte containing additive, and LiMnO4 positive electrode initial discharge specific capacity is that 139.7mAh/g, 0.1C charge and discharge cycles is after 40 weeks, specific capacity is 99.8mAh/g, and capability retention is 71.4%.And under equal conditions for adopting in the pure LiBETI-EC-DMC-DEC electrolyte of additive, LiCoPO4 positive electrode initial discharge specific capacity is 121.8mAh/g, and 0.1C charge and discharge cycles is after 45 weeks, and specific capacity is 20.4mAh/g, and capability retention is 16.7%.Illustrate and adopt containing the electrolyte of additive, LiCoPO4 positive electrode under high pressure discharge capacity and cycle performance is obtained for and significantly improves.
Claims (1)
1. voltage is a preparation method for the electrolyte of the new type lithium ion battery of 5V, it is characterized in that, concrete steps are as follows:
1) by ethylene carbonate EC, methyl ethyl carbonate and DEC purifying and mixing after dewatering respectively, mass ratio is 1: 2: 2, stirs, and above-mentioned carbonic ester mixed solvent and dipropylene glycol methyl ether acetate DPMA is mixed; Mass ratio is 1: 1, stirs and obtains mixed solvent;
2) be dissolved in above-mentioned mixed solvent by lithium salts LiBETI, described lithium salts is 1MOL/1L in the concentration of mixed solvent, stirs, and obtains not containing the electrolyte of additive;
3) additive is dissolved in above-mentioned not containing additive electrolyte in, the additive added is N, N-dimethyl trifluoroacetamide DTA, its percentage consumption is 3.5% of the electrolyte quality not containing additive, make it to dissolve, stir, obtaining is the electrolyte of 5V lithium ion battery for voltage.
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| CN201210055980.6A CN102683745B (en) | 2012-03-01 | 2012-03-01 | Voltage is the preparation method of the electrolyte of the new type lithium ion battery of 5V |
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Citations (2)
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|---|---|---|---|---|
| CN1228624A (en) * | 1998-03-11 | 1999-09-15 | 北京大学 | Lithium ion battery using high polymer pyrolytic carbon as negative pole |
| CN102361097A (en) * | 2011-11-14 | 2012-02-22 | 中国海洋石油总公司 | Preparation method of low-temperature electrolyte for lithium iron phosphate power battery |
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| WO2011024837A1 (en) * | 2009-08-28 | 2011-03-03 | 株式会社エクォス・リサーチ | Electrolyte for lithium-ion cell |
| CN102208678A (en) * | 2011-04-19 | 2011-10-05 | 中南大学 | Safe lithium ion battery |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1228624A (en) * | 1998-03-11 | 1999-09-15 | 北京大学 | Lithium ion battery using high polymer pyrolytic carbon as negative pole |
| CN102361097A (en) * | 2011-11-14 | 2012-02-22 | 中国海洋石油总公司 | Preparation method of low-temperature electrolyte for lithium iron phosphate power battery |
Non-Patent Citations (1)
| Title |
|---|
| 《Fluorinated organic solvents in electrolytes for lithium ion cells》;K.-C. Moller et al.;《Journal of Power Sources》;20011231;第97-98卷;595-597 * |
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