CN101304101A - Cylinder type lithium ion battery electrolytic solution and preparation method thereof - Google Patents
Cylinder type lithium ion battery electrolytic solution and preparation method thereof Download PDFInfo
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- CN101304101A CN101304101A CNA2008100293187A CN200810029318A CN101304101A CN 101304101 A CN101304101 A CN 101304101A CN A2008100293187 A CNA2008100293187 A CN A2008100293187A CN 200810029318 A CN200810029318 A CN 200810029318A CN 101304101 A CN101304101 A CN 101304101A
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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 invention provides a cylindrical lithium ion battery electrolyte, which consists of a lithium salt, an organic solvent and an additive, wherein, the mass ratios are respectively as follows: 12-17 percent of the lithium salt, 75-85 percent of the organic solvent and 3-8 percent of the additive. The preparation method for the cylindrical lithium ion battery electrolyte is that: the lithium salt, the organic solvent and the additive used in a lithium ion battery are reasonably combined, and the mass proportion is optimized, and then cylindrical lithium ion battery electrolyte is prepared through a reasonable technique. The obtained cylindrical lithium ion battery electrolyte satisfies the requirements of the capacity development, rate capability, the over-charging performance as well as the charge-discharge and the storage performance under high temperature of the cylindrical lithium ion battery, thus solving the described problems existing in the cylindrical lithium ion battery in the prior art.
Description
Technical field
The invention belongs to the lithium ion battery material technical field, relate to a kind of lithium-ion battery electrolytes that uses organic compound to form the optimum quality ratio performance, be specifically related to a kind of cylinder type lithium ion battery electrolytic solution and preparation method thereof.
Background technology
Lithium ion battery is widely used because of advantages such as its operating voltage height, specific energy is big, fail safe good, non-environmental-pollutions, and along with the development of lithium-ion electric pool technology, its performance index constantly are improved.The employed positive and negative pole material of lithium ion battery also develops to the diversification direction, develops into multiple composite transition metal and Nano type doff lithium oxide by single doff lithium oxide.Electrolyte also from liquid electrolyte to polymer dielectric and solid electrolyte and deposit development.
The lithium ion battery that needs in different commercial uses at present has different shapes, mainly contains square, Soft Roll shape and cylindrical battery.The purposes of battery is decided by self design advantage, and for example soft-package battery is applied in the model plane toy widely, and rectangular cell is applied in the battery of mobile phone widely, and cylindrical battery then is used in the power supplys such as notebook computer widely.Column lithium ion battery is most popular a kind of in the existing market, and its every battery performance also can both satisfy commercial use.But, because the special technological design of column lithium ion battery must be promoted the performance of its every performance by the electrolyte that adapts.For example, the both positive and negative polarity of lithium ion battery under the situation, requires electrolyte to can be good at being penetrated in the positive and negative pole material when high pressure.But the electrolyte of prior art can't well be penetrated in the battery plus-negative plate material, makes that every performance of column lithium ion battery is not well brought into play.
Summary of the invention
The purpose of this invention is to provide a kind of cylinder type lithium ion battery electrolytic solution and preparation method thereof, to have the employed lithium salts of lithium ion battery, organic solvent now, additive reasonably makes up and the quality optimization proportioning, the lithium-ion battery electrolytes that obtains by rational its preparation process, it has satisfied the needs with storge quality of discharging and recharging under capacity performance, high rate performance, over-charging and the hot conditions of column lithium ion battery, has solved the problems referred to above that column lithium ion battery exists in the prior art.
The invention provides a kind of cylinder type lithium ion battery electrolytic solution, it is made up of lithium salts, organic solvent and additive, and wherein the quality proportioning is respectively, lithium salts 12%～17%, organic solvent 75～85%, additive 3%～8%.
The present invention also provides a kind of cylinder type lithium ion battery electrolytic solution preparation method, and this method is carried out according to the following steps:
Step 1 will account for mass percent 75%～85% organic solvent in the process purification processes, and purity reaches more than 99.99%, and moisture≤10ppm joins in the reactor under the malleation inert gas shielding, through the abundant stirring and evenly mixing more than 1～3 hour;
Step 2 adds the electrolyte lithium salt LiPF that accounts for mass percent 11%～13% then
6, the temperature of hybrid reactor should be controlled at 15 ℃～30 ℃, continue to stir 1～3 hour;
Step 3 adds the electrolyte lithium salt that accounts for mass percent 1%～4% other type again after lithium salts fully dissolves, abundant stirring and evenly mixing under the same condition;
Step 4 adds 3%～8% different additive at last, and stirring and evenly mixing 6 hours～10 hours promptly gets cylinder type lithium ion battery electrolytic solution.
Lithium cylinder type lithium ion battery electrolytic solution of the present invention, its feature also be,
Described lithium salts is electrolyte lithium salt LiPF
6, the electrolyte lithium salt of described other type can be LiBF
4, LiBOB (di-oxalate lithium borate), LiTFSI[two (trifluoromethane sulfonic acid) imines lithium] in one or more.
Described organic solvent is: vinyl carbonate, propylene carbonate, methyl-propyl carbonic ester, dimethyl carbonate, diethyl carbonate, dipropyl carbonic ester, methyl-propyl carbonic ester and other sulfur-bearing, Halogen or undersaturated cyclic organic carbonates class also can be r-butyrolactone, oxolane, acetonitrile and sulfone type organic.
Described additive is: VC (vinylene carbonate), BP (biphenyl), CHB (cyclohexyl benzene), ethylene sulfite and derivative thereof.
Cylinder type lithium ion battery electrolytic solution of the present invention, be optimum organization and the quality optimization proportioning that the employed lithium salts of lithium ion battery, organic solvent, additive are carried out again, by the lithium-ion battery electrolytes that rational process prepares, it has the following advantages:
One, it satisfies discharging and recharging and storge quality under capacity performance, high rate performance, over-charging and the hot conditions of column lithium ion battery.
Two, be a kind of can fine infiltration column lithium ion battery both positive and negative polarity and the electrolyte of diaphragm material, and do not influence other performance performance of battery.
Three, a kind of nonflammable electrolyte of electrolyte of the present invention has been guaranteed the security performance of electrolyte.
Four, electrolyte of the present invention meets the environment RoHS of European Union standard, is a kind of electrolyte with good environmental-protecting performance.
Embodiment
The present invention is described in detail below in conjunction with embodiment.
The invention provides a kind of cylinder type lithium ion battery electrolytic solution, it is made up of lithium salts, organic solvent and additive, and wherein the quality proportioning is respectively, lithium salts 12%～17%, organic solvent 75～85%, additive 3%～8%.
Lithium salts of the present invention is electrolyte lithium salt LiPF
6, the electrolyte lithium of described other type can be LiBF
4, LiBOB (di-oxalate lithium borate), LiTFSI[two (trifluoromethane sulfonic acid) imines lithium] in one or more.
Organic solvent of the present invention is: vinyl carbonate, propylene carbonate, methyl-propyl carbonic ester, dimethyl carbonate, diethyl carbonate, dipropyl carbonic ester, methyl-propyl carbonic ester and other sulfur-bearing, Halogen or undersaturated cyclic organic carbonates class also can be r-butyrolactone, oxolane, acetonitrile and sulfone type organic.
Additive of the present invention is: VC (vinylene carbonate), BP (biphenyl), CHB (cyclohexyl benzene), ethylene sulfite and derivative thereof.
The present invention also provides the cylinder type lithium ion battery electrolytic solution preparation method, and this method is carried out according to the following steps:
Step 1 will account for mass percent 75%～85% organic solvent in the process purification processes, and purity reaches more than 99.99%, and moisture≤10ppm joins in the reactor under the malleation inert gas shielding, through the abundant stirring and evenly mixing more than 1～3 hour;
Step 2 adds the electrolyte lithium salt LiPF that accounts for mass percent 11%～13% then
6, the temperature of hybrid reactor should be controlled at 15 ℃～30 ℃, continue to stir 1～3 hour;
Step 3 adds the electrolyte lithium salt that accounts for mass percent 1%～4% other type again after lithium salts fully dissolves, abundant stirring and evenly mixing under the same condition;
Step 4 adds 3%～8% different additive at last, and stirring and evenly mixing 6 hours～10 hours promptly gets cylinder type lithium ion battery electrolytic solution.
Embodiment
Embodiment 1
The 75% organic solvent EC, DMC, EMC that account for total weight according to 1: 3: 2 (wt%) abundant mixing and stirring, slowly added the lithium salts LiPF that accounts for total weight 17%
6Lithium salts to be added makes after it fully dissolves, and adds the additive VC that accounts for total weight 3% again, and adding accounts for the additive PS of total weight 5% through stirring after, it is stirred, promptly obtain lithium-ion battery electrolytes of the present invention after stirring.
Embodiment 2
The 80% organic solvent EC, DMC, EMC that account for total weight according to 1: 3: 2 (wt%) abundant mixing and stirring, slowly added the lithium salts LiPF that accounts for total weight 17%
6Lithium salts to be added makes after it fully dissolves, and adds the additive VC that accounts for total weight 1% again, stirs the back and adds the additive PS that accounts for total weight 2%, it is stirred, promptly obtain lithium-ion battery electrolytes of the present invention after stirring.
Embodiment 3
The 83% organic solvent EC, DMC, EMC that account for total weight according to 1: 3: 2 (wt%) abundant mixing and stirring, slowly added the lithium salts LiPF that accounts for total weight 14%
6Lithium salts to be added makes after it fully dissolves, and adds the additive VC that accounts for total weight 1% again, stirs the back and adds the additive PS that accounts for total weight 2%, it is stirred, promptly obtain lithium-ion battery electrolytes of the present invention after stirring.
Embodiment 4
The 80% organic solvent EC, DMC, EMC that account for total weight according to 1: 3: 2 (wt%) abundant mixing and stirring, slowly added the lithium salts LiPF that accounts for total weight 15%
6Add the 2% lithium salts LiTFSI that accounts for total weight then, lithium salts to be added makes after it fully dissolves, add the additive VC that accounts for total weight 1% again, stir the back and add the additive PS that accounts for total weight 2%, it is stirred, can obtain lithium-ion battery electrolytes of the present invention after stirring.
Embodiment 5
The 78% organic solvent EC, DMC, EMC that account for total weight according to 1: 2: 2 (wt%) abundant mixing and stirring, slowly added the lithium salts LiPF that accounts for total weight 15%
6Add the 1% lithium salts LiTFSI that accounts for total weight then, lithium salts to be added makes after it fully dissolves, add the additive VC that accounts for total weight 2% again, stir the back and add the additive PS that accounts for gross weight 4%, it is stirred, can obtain lithium-ion battery electrolytes of the present invention after stirring
Embodiment 6
The 85% organic solvent EC, DMC, EMC that account for total weight according to 1: 2: 2 (wt%) abundant mixing and stirring, slowly added the lithium salts LiPF that accounts for total weight 11%
6Add the 1% lithium salts LiTFSI that accounts for total weight then, lithium salts to be added makes after it fully dissolves, add the additive VC that accounts for total weight 1% again, stir the back and add the additive PS that accounts for total weight 2%, it is stirred, can obtain lithium-ion battery electrolytes of the present invention after stirring
Embodiment 7
The 80% organic solvent EC, DMC, EMC that account for total weight according to 1: 2: 2 (wt%) abundant mixing and stirring, slowly added the lithium salts LiPF that accounts for total weight 13%
6Add the 1% lithium salts LiTFSI that accounts for total weight then, lithium salts to be added makes after it fully dissolves, add the additive VC that accounts for total weight 2% again, stir the back and add the additive PS that accounts for total weight 4%, it is stirred, can obtain lithium-ion battery electrolytes of the present invention after stirring.
Embodiment 8
The 83% organic solvent EC, DMC, EMC that account for total weight according to 1: 2: 2 (wt%) abundant mixing and stirring, slowly added the lithium salts LiPF that accounts for total weight 11%
6Add the 1% lithium salts LiTFSI that accounts for total weight then, lithium salts to be added makes after it fully dissolves, add the additive VC that accounts for total weight 1% again, stir the back and add the additive ES that accounts for total weight 2%, stir the back and add 2% the addition of C HB account for total weight, it is stirred, can obtain lithium-ion battery electrolytes of the present invention after stirring.
Electrolyte of the present invention also must be noted following link in the preparation process of organic solvent:
In glove box or the preparation of carrying out in the closed environment of other following condition that satisfies.Environmental requirement: moisture H
2O＜10ppm, O
2＜10ppm, environment can be regulated at inert gas and pressure.Satisfying under the condition of this environmental condition, guarantee employed first hold the container of electrolyte and organic solvent DMC rinse that stirring tool can be prepared adding clean, the DMC solvent that adds required quality then, the EMC organic solvent that adds required quality again, two kinds of solvents under stirring, blender are stirred, and then add the EC solvent of required quality, with same mixing speed stirring three kinds of solvents are mixed fully, add required lithium salts again, the adding of lithium salts divides three times and at the uniform velocity adds, add and fashionablely should notice that the temperature that holds electrolyte container is controlled at 15 ℃～30 ℃, lithium salts adds the back that finishes and stirs half an hour, add additive VC then successively, PS, CHB, a kind of additive of every adding just need fully mix, and can make lithium-ion battery electrolytes required for the present invention.
The selected lithium salts of the present invention can become the SEI film in the carbon negative terminal surface, protects the layer structure of carbon negative pole fully.Simultaneously, also can be under the big current conditions of electrolyte, lithium ion source is provided, eliminate consequent concentration polarization, the selected lithium salts of what is more important can bear higher temperature conditions, and the internal resistance to battery increases influence not quite, does not also produce the generation that a large amount of gas causes situations such as battery bulging.
The used organic additive of the present invention is selected from VC, CHB, PS, ES.Wherein VC can be good at forming uniform SEI film in the carbon negative terminal surface; and be widely used in the electrolyte film for additive; electropolymerization can take place in CHB under higher current potential; stop proceeding of charging process; thereby reach over-charge protective; simultaneously also produce gas to a certain extent, the activated current blocking equipment, charging process finishes.PS (1, the 3-propane sultone) not only can use as film for additive, and can impel skin covering of the surface to form again under higher temperature, suppresses the gas that the decomposition of SEI film produces under the hot conditions.ES (ethylene sulfite) also is that use is many in the film for additive, can form fine and close skin covering of the surface, promotes the performance of cycle performance of battery.
Organic solvent of the present invention can be two or more of existing non-protonization inert organic solvents.Can be higher boiling point or lower boiling material, also can be that low viscosity and other satisfy the organic solvent of actual electrical performance need.For example can make and be selected from vinyl carbonate, propylene carbonate, methyl-propyl carbonic ester, dimethyl carbonate, diethyl carbonate, dipropyl carbonic ester, methyl-propyl carbonic ester and other sulfur-bearing, Halogen or undersaturated cyclic organic carbonates class, also can be r-butyrolactone, oxolane, acetonitrile and sulfone type organic, organic solvent of the present invention be that two or more that select in the above-mentioned solvent mixes.
Claims (5)
1, a kind of cylinder type lithium ion battery electrolytic solution is characterized in that, it is made up of lithium salts, organic solvent and additive, and wherein the quality proportioning is respectively, lithium salts 12%～17%, organic solvent 75～85%, additive 3%～8%.
2, a kind of cylinder type lithium ion battery electrolytic solution preparation method is characterized in that, this method is carried out according to the following steps:
Step 1 will account for mass percent 75%～85% organic solvent in the process purification processes, and purity reaches more than 99.99%, and moisture≤10ppm joins in the reactor under the malleation inert gas shielding, through the abundant stirring and evenly mixing more than 1～3 hour;
Step 2 adds the electrolyte lithium salt LiPF that accounts for mass percent 11%～13% then
6, the temperature of hybrid reactor should be controlled at 15 ℃～30 ℃, continue to stir 1～3 hour;
Step 3 adds the electrolyte lithium salt that accounts for mass percent 1%～4% other type again after lithium salts fully dissolves, abundant stirring and evenly mixing under the same condition;
Step 4 adds 3%～8% different additive at last, and stirring and evenly mixing 6 hours～10 hours promptly gets cylinder type lithium ion battery electrolytic solution.
3, lithium cylinder type lithium ion battery electrolytic solution according to claim 1 is characterized in that, described lithium salts is electrolyte lithium salt LiPF
6, the electrolyte lithium salt of described other type can be LiBF
4, LiBOB (di-oxalate lithium borate), LiTFSI[two (trifluoromethane sulfonic acid) imines lithium] in one or more.
4, lithium cylinder type lithium ion battery electrolytic solution according to claim 1, it is characterized in that, described organic solvent is: vinyl carbonate, propylene carbonate, methyl-propyl carbonic ester, dimethyl carbonate, diethyl carbonate, dipropyl carbonic ester, methyl-propyl carbonic ester and other sulfur-bearing, Halogen or undersaturated cyclic organic carbonates class also can be r-butyrolactone, oxolane, acetonitrile and sulfone type organic.
5, lithium cylinder type lithium ion battery electrolytic solution according to claim 1 is characterized in that, described additive is: VC (vinylene carbonate), BP (biphenyl), CHB (cyclohexyl benzene), ethylene sulfite and derivative thereof.
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| CNA2008100293187A CN101304101A (en) | 2008-07-09 | 2008-07-09 | Cylinder type lithium ion battery electrolytic solution and preparation method thereof |
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| CNA2008100293187A CN101304101A (en) | 2008-07-09 | 2008-07-09 | Cylinder type lithium ion battery electrolytic solution and preparation method thereof |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102265447A (en) * | 2008-12-23 | 2011-11-30 | 陶氏环球技术有限责任公司 | Battery electrolyte solutions containing aromatic phosphorus compounds |
| 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 |
| CN102403535A (en) * | 2011-12-01 | 2012-04-04 | 香河昆仑化学制品有限公司 | High-voltage lithium ion battery non-aqueous electrolyte and preparation method thereof |
| CN102496739A (en) * | 2011-11-14 | 2012-06-13 | 中国海洋石油总公司 | Non-aqueous electrolyte manufacturing method for high-magnification charge-discharge lithium power battery |
| CN102637899A (en) * | 2012-04-29 | 2012-08-15 | 上海贯裕能源科技有限公司 | Lithium ion battery |
| CN102769148A (en) * | 2012-06-21 | 2012-11-07 | 新乡市盛林能源有限公司 | High-power lithium ion battery electrolyte |
| CN103165939A (en) * | 2013-03-01 | 2013-06-19 | 合肥国轩高科动力能源股份公司 | High voltage electrolyte of lithium ion battery |
| CN104282942A (en) * | 2013-11-14 | 2015-01-14 | 上海图尔实业发展有限公司 | High-performance electrolyte and application of high-performance electrolyte in secondary battery |
| CN109449488A (en) * | 2018-11-27 | 2019-03-08 | 湖北诺邦科技股份有限公司 | A kind of lithium-ion-power cell high magnification electrolyte and preparation method |
| CN111048835A (en) * | 2019-12-05 | 2020-04-21 | 广东维都利新能源有限公司 | Overcharge-resistant electrolyte, secondary lithium battery adopting electrolyte and preparation method of overcharge-resistant electrolyte |
| CN111082146A (en) * | 2020-01-21 | 2020-04-28 | 大同新成新材料股份有限公司 | Electrolyte taking propylene carbonate as main solvent |
| CN116078768A (en) * | 2023-04-12 | 2023-05-09 | 江苏尚纯自动化技术有限公司 | Rinsing method of electrolyte storage barrel |
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2008
- 2008-07-09 CN CNA2008100293187A patent/CN101304101A/en active Pending
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| CN102265447B (en) * | 2008-12-23 | 2015-05-06 | 陶氏环球技术有限责任公司 | Battery electrolyte solutions containing aromatic phosphorus compounds |
| CN102265447A (en) * | 2008-12-23 | 2011-11-30 | 陶氏环球技术有限责任公司 | Battery electrolyte solutions containing aromatic phosphorus compounds |
| 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 |
| CN102496739A (en) * | 2011-11-14 | 2012-06-13 | 中国海洋石油总公司 | Non-aqueous electrolyte manufacturing method for high-magnification charge-discharge lithium power battery |
| CN102403535A (en) * | 2011-12-01 | 2012-04-04 | 香河昆仑化学制品有限公司 | High-voltage lithium ion battery non-aqueous electrolyte and preparation method thereof |
| CN102637899A (en) * | 2012-04-29 | 2012-08-15 | 上海贯裕能源科技有限公司 | Lithium ion battery |
| CN102769148A (en) * | 2012-06-21 | 2012-11-07 | 新乡市盛林能源有限公司 | High-power lithium ion battery electrolyte |
| CN103165939A (en) * | 2013-03-01 | 2013-06-19 | 合肥国轩高科动力能源股份公司 | High voltage electrolyte of lithium ion battery |
| CN104282942A (en) * | 2013-11-14 | 2015-01-14 | 上海图尔实业发展有限公司 | High-performance electrolyte and application of high-performance electrolyte in secondary battery |
| CN109449488A (en) * | 2018-11-27 | 2019-03-08 | 湖北诺邦科技股份有限公司 | A kind of lithium-ion-power cell high magnification electrolyte and preparation method |
| CN111048835A (en) * | 2019-12-05 | 2020-04-21 | 广东维都利新能源有限公司 | Overcharge-resistant electrolyte, secondary lithium battery adopting electrolyte and preparation method of overcharge-resistant electrolyte |
| CN111082146A (en) * | 2020-01-21 | 2020-04-28 | 大同新成新材料股份有限公司 | Electrolyte taking propylene carbonate as main solvent |
| CN116078768A (en) * | 2023-04-12 | 2023-05-09 | 江苏尚纯自动化技术有限公司 | Rinsing method of electrolyte storage barrel |
| CN116078768B (en) * | 2023-04-12 | 2023-06-27 | 江苏尚纯自动化技术有限公司 | Rinsing method of electrolyte storage barrel |
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Open date: 20081112 |