CN101350431A - Low temperature electrolytic solution for ferrous phosphate lithium ion battery - Google Patents
Low temperature electrolytic solution for ferrous phosphate lithium ion battery Download PDFInfo
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- CN101350431A CN101350431A CNA2008100303704A CN200810030370A CN101350431A CN 101350431 A CN101350431 A CN 101350431A CN A2008100303704 A CNA2008100303704 A CN A2008100303704A CN 200810030370 A CN200810030370 A CN 200810030370A CN 101350431 A CN101350431 A CN 101350431A
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- ion battery
- lithium ion
- ferrous phosphate
- phosphate lithium
- battery electrolyte
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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
Abstract
The invention relates to the field of lithium batteries, disclosing a low-temperature electrolyte applied to a LiFePO4 Li-ion battery. The electrolyte is composed of ethylene carbonate, propylene carbonate, ethyl butyrate, fluoroethylene carbonate, lithium bis(oxalate)borate and lithium hexafluorophosphate. The electrolyte can remarkably improve the electric performance of the LiFePO4 Li-ion battery under low temperature, and ensure sound cyclic performance of the battery.
Description
Technical field
The present invention relates to the lithium battery field, relate in particular to a kind of lithium-ion battery electrolytes.
Background technology
Because problems such as technology and cost, lithium ion battery rests in the use field of compact battery always, along with the critical material technology and the battery technology of lithium ion battery makes progress rapidly, be used for the vehicles, electrician's instrument, electrician's toy, electric consumption on lighting pond, the large-sized battery in electric ship field, battery pack and begin to popularize to daily life.
At present, can mainly contain as the large-sized battery in battery of electric vehicle field: VRLA battery, Ni-MH battery, nickel-cadmium cell and lithium rechargeable battery, and in actual applications, lead-acid battery, Ni-MH battery are used more extensive.
But, has unique application advantage from the chemical property lithium rechargeable battery, the secondary cell specific energy reaches more than the 120Wh/kg, cycle life is more than 1000 times, energy density is plumbic acid and Ni-MH battery 2 to 3 times, and cycle life also is longest-lived in the existing secondary cell system.The more important thing is that lithium ion battery does not contain poisonous heavy metal element, and reclaim simply, is the environmental protection battery, and therefore, it just progressively is being developed as the electrical source of power of electric automobile.
In present lithium ion battery, because LiFePO 4 (LiFePO
4) having: (theoretical capacity is 170mAh/g to the specific capacity cheap, nontoxic, that Environmental compatibility is good, rich in mineral resources, higher, energy density is 550Wh/kg) and higher operating voltage (3.2V), charging/discharging voltage change advantages such as mild, good cycle performance, high-temperature behavior and security performance be good, it is a kind of desirable anode material for lithium-ion batteries.
But, LiFePO 4 LiFePO
4Electron conductivity lower, especially at low temperatures, its electron conductivity is lower, electrical property is affected.
Therefore, if can improve LiFePO 4 LiFePO
4Ion battery can be widened its range of application greatly at the electrical property of low temperature environment.
Summary of the invention
The embodiment of the invention provides a kind of lithium-ion battery electrolytes, uses this electrolyte and can significantly improve ferrous phosphate lithium ion battery electrical property at low temperatures, makes battery have better cycle performance.
The lithium-ion battery electrolytes that the embodiment of the invention provides comprises: lithium hexafluoro phosphate, ethylene carbonate, ethyl butyrate, propene carbonate, dimethyl carbonate.
Alternatively, this electrolyte also comprises: film for additive.
Alternatively, described film for additive comprises: fluorinated ethylene carbonate, two oxalic acid borate lithium.
Alternatively, the weight proportion content of described fluorinated ethylene carbonate is 1～5%.
Alternatively, the weight proportion content of described pair of oxalic acid borate lithium is 1～5%.
Alternatively, the weight proportion content of described ethyl butyrate is 30～40%.
Alternatively, the weight proportion content of described propene carbonate is 5～10%.
Alternatively, the weight proportion content of described ethylene carbonate is 25～35%.
Alternatively, the weight proportion content of described dimethyl carbonate is 15～30%, and/or,
Alternatively, described hexafluorophosphoric acid lithium concentration is 0.7～1.0mol/L.
Alternatively, the purity of described each component is greater than 99.95%, and moisture quality percentage composition is less than 20/1000000ths.
Because this electrolyte also comprises the lower propene carbonate of fusing point, ethyl butyrate, can effectively improve the electric conductivity of electrolyte when low temperature.
Using this electrolyte in as the lithium ion battery of anode electrode, can guarantee that battery under lower temperature environments, still has electric conductivity preferably with LiFePO 4.
In addition, because this electrolyte includes film for additive, be such as but not limited to fluorinated ethylene carbonate, two oxalic acid borate lithium.In the process that battery changes into, film for additive forms passivating film (SEI film) on the positive and negative electrode surface of lithium battery respectively, and the generation of following situation can effectively be extenuated even prevent to this passivating film:
Ferric ion in the anode electrode is dissolved in electrolyte and becomes Zero-valent Iron and produce precipitation at the surface reduction of graphite cathode, causes anodal LiFePO
4Capacity attenuation is serious in cyclic process, influences the cycle performance of lithium battery.
In addition, this passivating film can also suppress propene carbonate and negative pole takes place to insert altogether, strengthens the cycle performance of lithium ion battery.
Embodiment
Describe the present invention in detail below in conjunction with specific embodiment, be used for explaining the present invention in this illustrative examples of the present invention and explanation, but not as a limitation of the invention.
Embodiment 1:
This low temperature electrolytic solution for ferrous phosphate lithium ion battery comprises: ethylene carbonate, dimethyl carbonate, lithium hexafluoro phosphate, ethyl butyrate, propene carbonate, fluorinated ethylene carbonate, two oxalic acid borate lithium.
Owing to comprise the lower propene carbonate of fusing point, ethyl butyrate in this electrolyte, can effectively improve the electric conductivity of electrolyte when low temperature.
Experimental results show that: when this electrolyte is being lower than-30 ℃, still has higher conductivity, guarantee ferrous phosphate lithium ion battery-30 ℃ of discharge capacities greater than 80% of 25 ℃ of discharge capacities of normal temperature ,-40 ℃ of discharge capacities greater than 60% of 25 ℃ of discharge capacities of normal temperature.
In addition, can also in this electrolyte, add film for additive, be such as but not limited to: fluorinated ethylene carbonate, two oxalic acid borate lithium.
In the process that battery changes into, film for additive can form passivating film (SEI film) on the positive and negative electrode surface of lithium battery respectively, this passivating film can effectively be extenuated, even prevent the generation of following situation: the ferric ion in the anode electrode is dissolved in electrolyte, and become Zero-valent Iron and produce precipitation at the surface reduction of graphite cathode, cause anodal LiFePO
4Capacity attenuation is serious in cyclic process, influences the cycle performance of lithium battery.Especially, when battery overcharges, perhaps under exterior storage, the more high higher temperature of applied environment temperature, guarantee the security performance of battery.
Because battery is in cyclic process, the capacity of battery keeps advantages of higher stability, can effectively reduce because the rated capacity of battery capacity and battery has big difference, cause user's the actual charging interval to surpass the charging interval of calculating, cause the generation of the situation of over-charging of battery, reduce overcharging various unexpected generation that causes, such as: the battery thermal runaway takes place, phenomenons such as on fire, blast take place, the fail safe that has improved battery.
To sum up, the electrolyte use present embodiment in as the lithium ion battery of anode electrode with LiFePO 4 can guarantee that battery under lower temperature environments, still has electric conductivity preferably, and have better cycle performance that in circulation security performance is good.
Embodiment 2:
As a kind of preferred embodiment, the ferrous phosphate lithium ion battery electrolyte of present embodiment comprises: lithium hexafluoro phosphate, ethylene carbonate, ethyl butyrate, propene carbonate, dimethyl carbonate, fluorinated ethylene carbonate, two oxalic acid borate lithium.Wherein the proportioning of each component is as follows:
The content of ethylene carbonate is 25～35w.t.%, the content of propene carbonate is 5～10w.t.%, the content of dimethyl carbonate is 15～30w.t.%, the content of ethyl butyrate is 30～40w.t.%, the content of fluorinated ethylene carbonate is 1～5w.t.%, the content of two oxalic acid borate lithiums is 1～5w.t.%, and the hexafluorophosphoric acid lithium concentration is 0.7～1.0mol/L.
In order to guarantee that lithium battery has high stability, wherein the purity of each component is greater than 99.95%, and the quality percentage composition of moisture is less than 20/1000000ths, and each component all reaches the battery SILVER REAGENT.
Because the adding of additive in the present embodiment, the filming function of film for additive has suppressed the effect with graphite cathode, therefore propylene carbonate ester content (bringing up to 20～30%) can be suitably improved, the low temperature performance of this lithium ion battery can be further improved.
And in the present embodiment, because the adding of additive in the present embodiment, can form the SEI film, can suppress the generation of hydrogen fluoride (HF), therefore (being reduced to concentration is 0.7～1.0mol/L) to have reduced the hexafluorophosphoric acid lithium content in the present embodiment, increase floride-free lithium salts: the content of two oxalic acid borate lithiums (its concentration is 1～5% for weight proportion content) helps improving the cycle performance of battery.
More than the technical scheme that the embodiment of the invention provided is described in detail, used specific case herein the principle and the execution mode of the embodiment of the invention are set forth, the explanation of above embodiment only is applicable to the principle that helps to understand the embodiment of the invention; Simultaneously, for one of ordinary skill in the art, according to the embodiment of the invention, the part that on embodiment and range of application, all can change, in sum, this description should not be construed as limitation of the present invention.
Claims (10)
1, a kind of ferrous phosphate lithium ion battery electrolyte is characterized in that, comprises: lithium hexafluoro phosphate, ethylene carbonate, ethyl butyrate, propene carbonate, dimethyl carbonate.
2, ferrous phosphate lithium ion battery electrolyte according to claim 1 is characterized in that, also comprises: film for additive.
3, ferrous phosphate lithium ion battery electrolyte according to claim 2 is characterized in that, described film for additive comprises: fluorinated ethylene carbonate, two oxalic acid borate lithium.
4, ferrous phosphate lithium ion battery electrolyte according to claim 3 is characterized in that, the weight proportion content of described fluorinated ethylene carbonate is 1～5%.
5, ferrous phosphate lithium ion battery electrolyte according to claim 3 is characterized in that, the weight proportion content of described pair of oxalic acid borate lithium is 1～5%.
6, ferrous phosphate lithium ion battery electrolyte according to claim 3 is characterized in that, the weight proportion content of described ethyl butyrate is 30～40%.
7, ferrous phosphate lithium ion battery electrolyte according to claim 3 is characterized in that, the weight proportion content of described propene carbonate is 5～10%.
8, ferrous phosphate lithium ion battery electrolyte according to claim 3 is characterized in that, the weight proportion content of described ethylene carbonate is 25～35%.
9, ferrous phosphate lithium ion battery electrolyte according to claim 3 is characterized in that, the weight proportion content of described dimethyl carbonate is 15～30%, and/or,
Described hexafluorophosphoric acid lithium concentration is 0.7～1.0mol/L.
According to the arbitrary described ferrous phosphate lithium ion battery electrolyte of claim 3 to 10, it is characterized in that 10, the purity of described each component is greater than 99.95%, moisture quality percentage composition is less than 20/1000000ths.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2008100303704A CN101350431A (en) | 2008-08-26 | 2008-08-26 | Low temperature electrolytic solution for ferrous phosphate lithium ion battery |
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|---|---|---|---|
| CNA2008100303704A CN101350431A (en) | 2008-08-26 | 2008-08-26 | Low temperature electrolytic solution for ferrous phosphate lithium ion battery |
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| CN101350431A true CN101350431A (en) | 2009-01-21 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101924240A (en) * | 2010-07-29 | 2010-12-22 | 东莞新能源科技有限公司 | Lithium ion battery |
| CN102097650A (en) * | 2009-12-11 | 2011-06-15 | 三洋电机株式会社 | Lithium secondary battery |
| 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 |
| CN104282949A (en) * | 2014-10-27 | 2015-01-14 | 江苏津谊新能源科技有限公司 | Manufacturing method of low-temperature lithium ion battery |
| CN104332649A (en) * | 2014-09-09 | 2015-02-04 | 上海纳米技术及应用国家工程研究中心有限公司 | Electrolyte, and preparation method and application thereof |
-
2008
- 2008-08-26 CN CNA2008100303704A patent/CN101350431A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102097650A (en) * | 2009-12-11 | 2011-06-15 | 三洋电机株式会社 | Lithium secondary battery |
| CN101924240A (en) * | 2010-07-29 | 2010-12-22 | 东莞新能源科技有限公司 | Lithium ion battery |
| 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 |
| CN104332649A (en) * | 2014-09-09 | 2015-02-04 | 上海纳米技术及应用国家工程研究中心有限公司 | Electrolyte, and preparation method and application thereof |
| CN104332649B (en) * | 2014-09-09 | 2016-12-07 | 上海纳米技术及应用国家工程研究中心有限公司 | A kind of electrolyte and its preparation method and application |
| CN104282949A (en) * | 2014-10-27 | 2015-01-14 | 江苏津谊新能源科技有限公司 | Manufacturing method of low-temperature lithium ion battery |
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Open date: 20090121 |