CN105811010B - A kind of lithium battery - Google Patents
A kind of lithium battery Download PDFInfo
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- CN105811010B CN105811010B CN201410848611.1A CN201410848611A CN105811010B CN 105811010 B CN105811010 B CN 105811010B CN 201410848611 A CN201410848611 A CN 201410848611A CN 105811010 B CN105811010 B CN 105811010B
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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
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Y02E60/10—Energy storage using batteries
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Abstract
The present invention relates to a kind of lithium batteries, including anode, cathode and electrolyte, electrolyte includes organic solvent and lithium salts, and the organic solvent includes the cyclic carbonate for accounting for the organic solvent gross mass 30% ~ 50%, the chain carboxylate for accounting for the organic solvent gross mass 50% ~ 70%.The improvement that the present invention passes through formula and dosage to organic solvent, so that the formula of electrolyte is simple, it is easily configured, also, electrolyte has good conductivity, can satisfy lithium ion battery in the circulation requirement of low temperature (< -20 DEG C), it can meet under room temperature (25 DEG C), the circulation requirement of lithium ion battery, meanwhile, it is capable to reach lithium ion battery in the performance requirement of high temperature (65 DEG C).
Description
Technical field
The invention belongs to electrochemical technology fields, and in particular to a kind of lithium battery.
Background technique
Energy density is high, power density is big, good cycle, memory-less effect, green ring due to having for lithium ion battery
The features such as guarantor, mobile communication equipment such as mobile phone, mobile camera, laptop, in mobile phone various electronic products
Be used widely, at the same be also the following electric car energy supplying system in strong candidate.Lithium battery electrolytes use
Chain organic solvent often have: dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, methyl propyl carbonate etc. and they two
Kind or a variety of mixtures, the lithium salts used usually have: lithium hexafluoro phosphate, lithium perchlorate, LiBF4, dioxalic acid close boric acid
Lithium, trifluoromethyl sulfonic acid lithium, double fluorine sulfimide lithiums etc. and their two or more mixtures.Due to propene carbonate
(PC) for the destruction of graphite cathode during circulating battery, people are compared with more options ethylene carbonate (EC).But due to
The high-melting-point (ca.30 DEG C) of ethylene carbonate, seriously affects the conductivity of electrolyte under low temperature, therefore the solvent of traditional electrolyte
The carbonic ester for generally mixing with ethylene carbonate (EC) and other low melting points, such as dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate
Deng and their two or more mixtures to meet the requirement of (Ca.-20 DEG C) under general lithium battery low temperature.
With lithium battery application field extension, need to develop new type low temperature electrolyte (ca.-40 DEG C or -60 DEG C),
Electrolyte must also conductivity with higher simultaneously.To keep electrolyte to have the characteristics of low temperature high conductivity, solvent is necessary
Selection and dimethyl carbonate (DMC), diethyl carbonate (DEC) and methyl ethyl carbonate (EMC) etc. have similar quality, but fusing point is more
Low carboxylate solvent.
2008, the carboxylates such as Central South University's formic acid methyl esters (MF), gamma-butyrolacton (GBL) were prepared as additive
Low temperature electrolytes for Li-ion batteries (application number: CN200810030976.8)；
2012, Huzhou Chuangya Power Battery Materials Co., Ltd proposed using nitrogen-containing heterocycles aryl such as C5H5N and its spreads out
Biology prepares low temperature electrolytes for Li-ion batteries (publication number: CN103078136A) as low temperature additive；
2012, Li electricity Co., Ltd of Air China prepared low temperature electrolytes for Li-ion batteries using ethyl acetate (EA) as low
One of warm four kinds of solution of electrolyte.
But the cryogenic property and conductivity of the lithium battery of above-mentioned electrolyte preparation cannot still be met the requirements.
Summary of the invention
Technical problem to be solved by the invention is to provide a kind of lithium batteries with the high conductivity of low temperature.
In order to achieve the above objectives, the technical solution adopted by the present invention is that:
A kind of lithium battery, including anode, cathode and electrolyte, the electrolyte include organic solvent and lithium salts, described
Organic solvent include the cyclic carbonate for accounting for the organic solvent gross mass 30%~50%, to account for the organic solvent total
The chain carboxylate of quality 50%~70%, the structural formula of the chain carboxylate are as follows:
Wherein, alkyl, the alkoxy, haloalkoxy of A, B independently selected from carbon atom number for 1~10
Base, halogenated alkyl, alkylene, phenyl, xenyl, halogenophenyl, any one in halogenated biphenyl base, in which: halogen F,
Cl or Br, it is halogenated to replace for part or all replace.
Preferably, the cyclic carbonate accounts for the 30%~40% of the organic solvent gross mass, the chain
Carboxylate accounts for the 60%~70% of the organic solvent gross mass.
It is further preferred that the cyclic carbonate accounts for the 35%~40% of the organic solvent gross mass, it is described
Chain carboxylate account for the 60%~65% of the organic solvent gross mass.
Preferably, the cyclic carbonate is sub- selected from ethylene carbonate, propene carbonate, gamma-butyrolacton and carbonic acid
One of butyl ester.
Preferably, the chain carboxylate is selected from methyl formate, Ethyl formate, propyl formate, butyl formate, acetic acid
Methyl esters, ethyl acetate, propyl acetate, butyl acetate, methyl propionate, ethyl propionate, propyl propionate, butyl propionate, methyl butyrate,
One of ethyl butyrate, propyl butyrate, butyl butyrate.
Preferably, the concentration of the lithium salts is 0.001~2mol/L, and the lithium salts is LiBF4、LiPF6、LiAsF6、
LiClO4、LiN(SO2CF3)2、LiN(SO2C2F5)2、LiSO3CF3、LiC2O4BC2O4、LiFC6F5BC2O4One of or it is a variety of.
Preferably, the low-temperature electrolyte further includes the additive for accounting for the electrolyte gross mass 1%~10%.
Preferably, the additive is selected from biphenyl, vinylene carbonate, vinylethylene carbonate, fluoro carbonic acid second
Enester, propylene sulfite, butylene sulfite, 1,3- propane sultone, ethylene sulfite, sulfuric acid vinyl ester, cyclohexyl
One of benzene, tert-butyl benzene, succinonitrile are a variety of.
Preferably, the material of the anode includes: the active material LiCoO of mass content 92%~96%2, quality contains
The binder PVDF of the carbon black of amount 2%~4%, mass content 1%~4%, collector is aluminium foil, pole piece 4~4.5cm of width,
0.1~0.2mm of thickness；
The material of the cathode includes: the active material artificial graphite of mass content 92%~96%, mass content 1%
The binder CMC of~4% conductive carbon SP, mass content 2%~4%, collector are copper foil, and pole piece 4~4.5cm of width is thick
Spend 0.1~0.2mm.
Preferably, the lithium battery further includes diaphragm, and the diaphragm is tri- one polymer film of PE/PP/PE.
The lithium battery includes lithium primary battery, lithium secondary battery and lithium ion battery.
Due to the above technical solutions, the present invention has the following advantages over the prior art:
The present invention is easily configured by the improvement of formula and dosage to organic solvent so that the formula of electrolyte is simple,
Also, electrolyte has good conductivity, can satisfy lithium ion battery in the circulation requirement of low temperature (< -20 DEG C), Neng Goufu
It closes under room temperature (25 DEG C), the circulation requirement of lithium ion battery, meanwhile, it is capable to reach lithium ion battery in the performance of high temperature (65 DEG C)
It is required that.
Detailed description of the invention
Attached drawing 1 is the cyclic voltammogram of comparative example 1 and embodiment 1；
Specific embodiment
It elaborates below in conjunction with specific embodiment to the present invention:
Comparative example 1
By weight 30% ethylene carbonate (EC), 70% methyl ethyl carbonate (EMC) is taken respectively, in humidity less than 1%
In glove box, it is sufficiently mixed uniformly, is configured to electrolyte solvent.Then, the electrolytic salt that total amount is 1mol/L is added by several times
LiPF6, after stirring half an hour, matter salt to be electrolysed sufficiently dissolves, and shelves 24 hours；Up to electrolyte.
Electrolyte, which is filled, carries out flash-over characteristic detection, used battery in battery are as follows:
Anode: active material LiCoO2Mass content 95%, carbon black 3%, binder PVDF2%, aluminium foil is collector.
Pole piece width 4.2cm, thickness 0.15mm；
Cathode: the mass content 95% of active material artificial graphite, conductive carbon SP 2%, binder CMC 3%, copper foil are
Collector, pole piece width are 4.3cm, thickness 0.18mm；
Diaphragm is tri- one polymer film of PE/PP/PE；Battery capacity is 1575mAh.
Comparative example 2
By weight 40% ethylene carbonate (EC), 60% methyl ethyl carbonate (EMC) is taken respectively, in humidity less than 1%
In glove box, it is sufficiently mixed uniformly, is configured to electrolyte solvent.Then, the electrolytic salt that total amount is 1mol/L is added by several times
LiPF6, after stirring half an hour, matter salt to be electrolysed sufficiently dissolves, and shelves 24 hours；Up to electrolyte.The battery used is the same as comparison
Example 1.
Comparative example 3
By weight 30% ethylene carbonate (EC), 70% methyl ethyl carbonate (EMC) is taken respectively, in humidity less than 1%
In glove box, it is sufficiently mixed uniformly, is configured to electrolyte solvent.Then, the electrolytic salt that total amount is 1mol/L is added by several times
LiPF6, matter salt to be electrolysed sufficiently dissolves；Under stirring conditions, the vinylene carbonate for accounting for electrolyte gross mass 1% is sequentially added
Ester (VC) and 1% 1,3-propane sultone (PS), stir half an hour after, shelve 24 hours；Up to electrolyte.The battery used
With comparative example 1.
Comparative example 4
Ethylene carbonate (EC), dimethyl carbonate (DMC), ethyl acetate (EA) are weighed by weight 1:1:1, it is small in humidity
In 1% glove box, it is sufficiently mixed uniformly, is configured to electrolyte solvent.Then, the electrolysis that total amount is 1mol/L is added by several times
Matter salt LiPF6, after stirring half an hour, matter salt to be electrolysed sufficiently dissolves, and shelves 24 hours；Up to electrolyte.The battery used is same
Comparative example 1.
Comparative example 5
By weight 20% ethylene carbonate (EC), 80% ethyl acetate (EA) is taken respectively, in gloves of the humidity less than 1%
In case, it is sufficiently mixed uniformly, is configured to electrolyte solvent.Then, the electrolytic salt LiPF6 that total amount is 1mol/L is added by several times,
After stirring half an hour, matter salt to be electrolysed sufficiently dissolves, and shelves 24 hours；Up to electrolyte.The battery used is the same as comparative example 1.
Comparative example 6
By weight 50% ethylene carbonate (EC), 50% ethyl acetate (EA) is taken respectively, in gloves of the humidity less than 1%
In case, it is sufficiently mixed uniformly, is configured to electrolyte solvent.Then, the electrolytic salt LiPF6 that total amount is 1mol/L is added by several times,
After stirring half an hour, matter salt to be electrolysed sufficiently dissolves, and shelves 24 hours；Up to electrolyte.The battery used is the same as comparative example 1.
Embodiment 1
By weight 30% ethylene carbonate (EC), 70% ethyl acetate (EA) is taken respectively, in gloves of the humidity less than 1%
In case, it is sufficiently mixed uniformly, is configured to electrolyte solvent.Then, the electrolytic salt LiPF that total amount is 1mol/L is added by several times6,
After stirring half an hour, matter salt to be electrolysed sufficiently dissolves, and shelves 24 hours；Up to low-temperature electrolyte.The same comparative example of the battery used
1。
Embodiment 2
By weight 30% ethylene carbonate (EC), 70% ethyl acetate (EA) is taken respectively, in gloves of the humidity less than 1%
In case, it is sufficiently mixed uniformly, is configured to electrolyte solvent.Then, the electrolytic salt LiPF that total amount is 1mol/L is added by several times6,
Matter salt to be electrolysed sufficiently dissolves, and the vinylene carbonate acid (VC) for being added 1% shelves 24 hours after stirring half an hour to get low temperature
Electrolyte.The battery used is the same as comparative example 1.
Embodiment 3
By weight 40% ethylene carbonate (EC), 60% ethyl acetate (EA) is taken respectively, in gloves of the humidity less than 1%
In case, it is sufficiently mixed uniformly, is configured to electrolyte solvent.Then, the electrolytic salt LiPF that total amount is 1mol/L is added by several times6,
After stirring half an hour, matter salt to be electrolysed sufficiently dissolves, and shelves 24 hours；Up to low-temperature electrolyte.The same comparative example of the battery used
1。
Embodiment 4
By weight 40% ethylene carbonate (EC), 60% ethyl acetate (EA) is taken respectively, in gloves of the humidity less than 1%
In case, it is sufficiently mixed uniformly, is configured to electrolyte solvent.Then, the electrolytic salt LiPF that total amount is 1mol/L is added by several times6,
Matter salt to be electrolysed sufficiently dissolves, and the vinylene carbonate acid (VC) for being added 1% shelves 24 hours after stirring half an hour to get low temperature
Electrolyte.The battery used is the same as comparative example 1.
Embodiment 5
By weight 30% ethylene carbonate (EC), 70% ethyl acetate (EA) is taken respectively, in gloves of the temperature less than 1%
In case, it is sufficiently mixed uniformly, is configured to electrolyte solvent.Then, the electrolytic salt LiPF that total amount is 1mol/L is added by several times6,
Matter salt to be electrolysed sufficiently dissolves；Under stirring conditions, 1% vinylene carbonate sour (VC) and 1% 1,3- third are sequentially added
Alkane sultone (PS) is shelved 24 hours after stirring half an hour；Up to low-temperature electrolyte.The battery used is the same as comparative example 1
Embodiment 6
By weight 30% ethylene carbonate (EC), 70% methyl propionate (MP) is taken respectively, in gloves of the humidity less than 1%
In case, it is sufficiently mixed uniformly, is configured to electrolyte solvent.Then, the electrolytic salt LiPF that total amount is 1mol/L is added by several times6,
Matter salt to be electrolysed sufficiently dissolves；Under stirring conditions, 1% vinylene carbonate sour (VC) and 1% 1,3- third are sequentially added
Alkane sultone (PS) is shelved 24 hours after stirring half an hour；Up to low-temperature electrolyte.The battery used is the same as comparative example 1.
Embodiment 7
By weight 35% ethylene carbonate (EC), 65% ethyl acetate (EA) is taken respectively, in gloves of the humidity less than 1%
In case, it is sufficiently mixed uniformly, is configured to electrolyte solvent.Then, the electrolytic salt LiPF that total amount is 1mol/L is added by several times6,
Matter salt to be electrolysed sufficiently dissolves；Under stirring conditions, 1% vinylene carbonate sour (VC) and 1% 1,3- third are sequentially added
Alkane sultone (PS) is shelved 24 hours after stirring half an hour；Up to low-temperature electrolyte 4.The battery used is the same as comparative example 1.
Embodiment 8
By weight 40% ethylene carbonate (EC), 60% ethyl acetate (EA) is taken respectively, in gloves of the humidity less than 1%
In case, it is sufficiently mixed uniformly, is configured to electrolyte solvent.Then, the electrolytic salt LiPF that total amount is 1mol/L is added by several times6,
Matter salt to be electrolysed sufficiently dissolves；Under stirring conditions, 1% vinylene carbonate sour (VC) and 1% 1,3- third are sequentially added
Alkane sultone (PS) is shelved 24 hours after stirring half an hour；Up to low-temperature electrolyte.The battery used is the same as comparative example 1.
Embodiment 9
By weight 35% ethylene carbonate (EC), 65% methyl propionate (MP) is taken respectively, in gloves of the humidity less than 1%
In case, it is sufficiently mixed uniformly, is configured to electrolyte solvent.Then, the electrolytic salt LiPF that total amount is 1mol/L is added by several times6,
Matter salt to be electrolysed sufficiently dissolves；Under stirring conditions, 1% vinylene carbonate sour (VC) and 1% 1,3- third are sequentially added
Alkane sultone (PS) is shelved 24 hours after stirring half an hour；Up to low-temperature electrolyte.The battery used is the same as comparative example 1.
Embodiment 10
By weight 40% ethylene carbonate (EC), 60% methyl propionate (MP) is taken respectively, in gloves of the humidity less than 1%
In case, it is sufficiently mixed uniformly, is configured to electrolyte solvent.Then, the electrolytic salt LiPF that total amount is 1mol/L is added by several times6,
Matter salt to be electrolysed sufficiently dissolves；Under stirring conditions, 1% vinylene carbonate sour (VC) and 1% 1,3- third are sequentially added
Alkane sultone (PS) is shelved 24 hours after stirring half an hour；Up to low-temperature electrolyte.The battery used is the same as comparative example 1.
The present invention enumerates under low temperature in table form, and the conductivity of electrolyte in comparative example and embodiment, see Table 1 for details.
Table 1
Wherein, "-": indicate that electrolytic salt is precipitated in electrolyte, conductivity can not measure.
Table 2 is the chemical property of the battery of each comparative example and embodiment.
Table 2
The above embodiments merely illustrate the technical concept and features of the present invention, and its object is to allow person skilled in the art
Scholar cans understand the content of the present invention and implement it accordingly, and it is not intended to limit the scope of the present invention, it is all according to the present invention
Equivalent change or modification made by Spirit Essence, should be covered by the protection scope of the present invention.
Claims (5)
1. a kind of lithium battery, including anode, cathode and electrolyte, the electrolyte include organic solvent and lithium salts, feature
Be: the organic solvent is by accounting for the cyclic carbonate of the organic solvent gross mass 30% ~ 40% and accounting for described organic molten
The chain carboxylate of agent gross mass 60% ~ 70% forms, and the cyclic carbonate is ethylene carbonate, the chain carboxylate
For ethyl acetate or methyl propionate；And linear carbonate is not contained in the electrolyte；The material of the anode includes: matter
Measure the active material LiCoO of content 92% ~ 96%2, the carbon black of mass content 2% ~ 4%, mass content 1% ~ 4% binder PVDF,
Collector is aluminium foil, pole piece width 4 ~ 4.5 cm, 0.1 ~ 0.2mm of thickness;
The material of the cathode includes: that the active material artificial graphite of mass content 92% ~ 96%, mass content 1% ~ 4% are led
The binder CMC of electrical carbon SP, mass content 2% ~ 4%, collector are copper foil, pole piece width 4 ~ 4.5 cm, 0.1 ~ 0.2mm of thickness；
The lithium battery further includes diaphragm, and the diaphragm is tri- one polymer film of PE/PP/PE.
2. lithium battery according to claim 1, it is characterised in that: it is total that the cyclic carbonate accounts for the organic solvent
The 35% ~ 40% of quality, the chain carboxylate account for the 60% ~ 65% of the organic solvent gross mass.
3. lithium battery according to any one of claim 1 to 2, it is characterised in that: the concentration of the lithium salts is
0.001 ~ 2 mol/L, the lithium salts are LiBF4、LiPF6、LiAsF6、LiClO4、LiN(SO2CF3)2、LiN(SO2C2F5)2、
LiSO3CF3、LiC2O4BC2O4、LiFC6F5BC2O4One of or it is a variety of.
4. lithium battery according to any one of claim 1 to 2, it is characterised in that: the electrolyte further includes accounting for institute
The additive for the electrolyte gross mass 1% ~ 10% stated.
5. lithium battery according to claim 4, it is characterised in that: the additive is selected from biphenyl, vinylene carbonate
Ester, vinylethylene carbonate, fluorinated ethylene carbonate, propylene sulfite, butylene sulfite, 1,3- propane sultone, Asia
One of sulfuric acid vinyl ester, sulfuric acid vinyl ester, cyclohexyl benzene, tert-butyl benzene, succinonitrile are a variety of.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| EP3694039A1 (en) * | 2019-02-07 | 2020-08-12 | Saft America | Electrolyte for low temperature operation of lithium titanate electrode, graphite electrodes, and lithium-ion batteries |
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| CN107666011B (en) * | 2016-07-28 | 2020-07-28 | 微宏动力系统（湖州）有限公司 | Non-aqueous electrolyte and non-aqueous electrolyte secondary battery |
| CN107293787A (en) * | 2017-06-21 | 2017-10-24 | 颍上北方动力新能源有限公司 | A kind of formula of environmentally friendly lithium battery electrolytes and preparation method thereof |
| CN109119631B (en) * | 2017-06-26 | 2021-09-21 | 宁德时代新能源科技股份有限公司 | Secondary battery |
| CN111224161B (en) * | 2018-11-26 | 2021-06-15 | 中国科学院大连化学物理研究所 | Method for improving low-temperature service performance of lithium ion battery by electrolyte containing additive |
| CN110556549B (en) * | 2019-08-21 | 2022-07-08 | 天津大学 | Lithium primary battery |
| WO2022016378A1 (en) * | 2020-07-21 | 2022-01-27 | 宁德新能源科技有限公司 | Battery and electronic device |
| CN112164826A (en) * | 2020-09-29 | 2021-01-01 | 中国科学院长春应用化学研究所 | Low-temperature electrolyte of double-ion battery and double-ion battery |
| CN113363671B (en) * | 2021-06-30 | 2024-01-30 | 宁德新能源科技有限公司 | Electrochemical device and electronic device |
| GB2625308A (en) * | 2022-12-13 | 2024-06-19 | Dyson Technology Ltd | Electrolyte composition |
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| CN102306837B (en) * | 2011-08-08 | 2014-11-19 | 珠海市赛纬电子材料有限公司 | Electrolyte solution of lithium ion battery |
| JP6035776B2 (en) * | 2012-02-24 | 2016-11-30 | 三菱化学株式会社 | Non-aqueous electrolyte and lithium secondary battery using the same |
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| CN103078141A (en) * | 2013-01-25 | 2013-05-01 | 宁德新能源科技有限公司 | Lithium-ion secondary battery and electrolyte thereof |
| CN103985906A (en) * | 2014-06-06 | 2014-08-13 | 东莞市杉杉电池材料有限公司 | Lithium ion battery electrolyte with both high and low temperature performances |
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| EP3694039A1 (en) * | 2019-02-07 | 2020-08-12 | Saft America | Electrolyte for low temperature operation of lithium titanate electrode, graphite electrodes, and lithium-ion batteries |
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