CN102340006A - Method for improving low-temperature performance of power lithium ion battery at different low-temperature environments - Google Patents
Method for improving low-temperature performance of power lithium ion battery at different low-temperature environments Download PDFInfo
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- CN102340006A CN102340006A CN2011102938713A CN201110293871A CN102340006A CN 102340006 A CN102340006 A CN 102340006A CN 2011102938713 A CN2011102938713 A CN 2011102938713A CN 201110293871 A CN201110293871 A CN 201110293871A CN 102340006 A CN102340006 A CN 102340006A
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Abstract
The invention aims to provide a method for improving a low-temperature performance of a power lithium ion battery at different low-temperature environments and is proposed based on factors influencing the low-temperature performance of the lithium ion battery. According to proposals in the invention, major factors influencing the lower-temperature performance of the lithium ion battery are different at different temperature environments, the major factor influencing the low-temperature performance of the lithium ion battery at 25-(-5) DEG C is the diffusion capability of lithium ions in an active substance, and the major factor influencing the low-temperature performance of the lithium ion battery at the temperature below -5 DEG C is the electric conductivity of the lithium ions in electrolyte. The invention provides the more specific, effective and economic method for solving the problem on the low-temperature performance of the lithium ion battery.
Description
Technical field
The present invention relates to improve the method for power lithium-ion battery cryogenic property, specifically a kind of process of improving the lithium ion battery cryogenic property.
Background technology
Lithium ion battery just is widely used in every field because of having characteristics such as light weight, specific energy height and life-span length once the marketization.Also to the higher requirement of performance proposition of lithium ion battery, not only require its cycle life, high rate charge-discharge performance of having high specific energy at normal temperatures, growing, and require it to possess same performance at low temperatures simultaneously.Cryogenic property that it is generally acknowledged lithium ion battery is mainly determined by the diffusivity in conductive capability, electrode interface and the battery active material of lithium ion in electrolyte.Researcher mostly is devoted to the developmental research of low-temperature electrolyte at present; The minority bibliographical information was also arranged in recent years through changing the cryogenic property that conductive agent changes lithium ion battery; But the cryogenic property of lithium ion battery can only obtain raising to a certain degree; Do not have the interim influencing factor of lithium ion battery cryogenic property under the more concrete research low temperature, thereby fail to propose the cryogenic property that effective method more improves lithium ion battery.The present invention proposes a kind of temperature environment according to lithium ion battery work and uses more suitable, effective, economic scheme to improve the method for lithium ion battery cryogenic property.
Summary of the invention
The present invention solves the low technical problem that waits of lithium ion battery charge-discharge performance under the existing in prior technology low temperature environment; Done further analysis from principle; It is a kind of more reasonable to propose; Effectively, the method for economic raising lithium ion battery cryogenic property, be to existing a kind of raisings that improves lithium ion battery cryogenic property method and additional.
Realization of the present invention mainly is a cryogenic property of improving lithium ion battery through the kind of kind that changes conductive agent and electrolyte.Confirming under the temperature environment of lithium ion battery work, using more directly, effective method and reach the more cost effective purpose of improving the lithium ion battery cryogenic property.Specifically, if battery is under 25 ℃～-5 ℃ temperature environments, to work, the kind that then only need change conductive agent is about to the graininess conductive agent and is changed to the wire conductive agent, and need not to change the kind of electrolyte, and normal temperature type electrolyte gets final product.If work under the low temperature environment below-5 ℃; Change the kind of conductive agent when can change the cryogenic property of lithium ion battery this moment through the kind of independent change electrolyte or changing the electrolyte kind; Be about to the graininess conductive agent and be changed to the wire conductive agent; Normal temperature electrolyte is changed to low temperature electrolytic solution, and this moment, battery can be effectively utilized more.
It is generally acknowledged that the principal element that influences the lithium ion battery cryogenic property is the diffusivity in conductive capability, electrode interface and the battery active material of lithium ion in electrolyte etc.The kind that the present invention changes conductive agent promptly is to change the diffusivity of lithium ion in battery active material, and the kind that changes electrolyte promptly is to change the conductive capability of lithium ion in electrolyte, thereby changes the cryogenic property of lithium ion battery.
Under general low temperature (25～-5 ℃) condition; The conductive capability of lithium ion in normal temperature type electrolyte is also unaffected, and (conductive capability of lithium ion in electrolyte mainly receives the influence of the solidifying point of organic solvent in the electrolyte; And the solidifying point of generally forming the organic compound of electrolyte all will be lower than-5 ℃); And lithium ion must be crossed the interfacial potential energy barrier of particle contact in electrode active material; But the energy of lithium ion is lower under low temperature (below the 25 ℃) condition; The probability of interfacial potential energy barrier of crossing particle contact is very little, and the principal element that influence the lithium ion battery cryogenic property this moment is the diffusivity of lithium ion in electrode active material, can change the diffusivity of lithium ion in electrode active material through the kind that changes conductive agent.
Present widely used conductive agent is conductive black, acetylene black and SP etc.; Electrical conduction mechanism mainly is through direct contact or in-plant tunnel effect conduction; Because these conductive agents all are graininess; In the less space that sinks into easily to form of draw ratio, can not form continuous conductive channel by active material.And the wire conductive agent especially the hollow structure of one dimension CNT have the effect that liquid is protected in imbibition; For the transmission of lithium ion in electrode active material provides good liquid environment and path, reduced its resistance in diffusion process, the draw ratio of wire conductive agent is bigger simultaneously; Can realize micron-sized connection; One can be played hundreds of to the conduction distance that several thousand conductive particles just can reach, and in active material, can form conductive network, reduces surface resistivity; Improve the migration rate of electronics, ion, thereby increased active material conductive capability at low temperatures.
Under the cryogenic conditions below-5 ℃; Because temperature is low more more near the solidifying point of organic substance; Cause the conductive capability of lithium ion in electrolyte to be obstructed, the factor that influences the lithium ion battery cryogenic property this moment also receives the influence of the conductive capability of lithium ion in electrolyte except the diffusivity of lithium ion in electrode active material.Electrolyte generally is made up of organic substance; Because physical propertys such as the dielectric constant of each organic substance, viscosity, solidifying point have nothing in common with each other; Conductive capability also is not quite similar under the different temperature environment, so under the cryogenic conditions below-5 ℃, can improve the conductive capability of lithium ion in electrolyte and the diffusivity in electrode active material through the kind that changes conductive agent in kind that changes electrolyte or the kind that changes electrolyte.
Embodiment
1.25 ℃～-5 ℃ of batteries that low temperature environment is worked down; General graininess conductive agent in anodal (or negative pole) is changed to CNT (or carbon fiber) conductive agent; Through stirring, be coated with, cut, reel and process electric core; Annotate normal temperature type electrolyte, the alclad plastic film is after change into, become to process flexible packing lithium ion battery behind the partial volume.The battery of low temperature environment work below-5 ℃ is processed flexible packing lithium ion battery by above general technology method, just the general graininess conductive agent in anodal (or negative pole) is changed to CNT (or carbon fiber) conductive agent, and electric core is annotated low-temperature electrolyte.
2.25 ℃～-5 ℃ of batteries that low temperature environment is worked down, process flexible packing lithium ion battery by the process in 1, just the general graininess conductive agent in the both positive and negative polarity is changed to CNT or (carbon fiber) conductive agent, electric core is annotated general electrolyte.The battery of environmental work below-5 ℃ is processed flexible packing lithium ion battery by the process in 1, just the general graininess conductive agent in the both positive and negative polarity is changed to CNT (or carbon fiber) conductive agent, and electric core is annotated low-temperature electrolyte.
3.-5 the battery of environmental work below ℃ is processed flexible packing lithium ion battery by the process in 1, just the conductive agent in the both positive and negative polarity is all used general graininess conductive agent, and electric core is annotated low temperature electrolytic solution.
Embodiment 1
With positive active material LiMn
2O
4, conductive agent CNT, binding agent LA133 be by 95.5: 1.5: 3 mixed; Negative electrode active material native graphite, conductive agent CNT, binding agent LA133 press 96: 1: 3 mixed; Technical process in 1 is processed electric core, and it is LiPF that electric core is annotated electrolytic salt
6Normal temperature type electrolyte, process flexible packing lithium ion battery.Through changing into, behind the partial volume, in the safe scholar's extra-high-speed low-temperature test chamber of Nanjing, carry out 0 ℃ ,-5 ℃ ,-10 ℃ low-temperature tests respectively, it is following that test data low temperature discharge capacity accounts for the percentage of normal temperature discharge capacity:
| Probe temperature | 0℃ | -5℃ | -10℃ |
| Low temperature/normal temperature discharge capacity | 94.39％ | 89.93％ | 75.05％ |
Embodiment 2
With positive active material LiMn
2O
4, conductive agent CNT, binding agent LA133 be by 94: 3: 3 mixed; Negative electrode active material native graphite, conductive agent CNT, binding agent LA133 press 95: 2: 3 mixed; Technical process in 1 is processed electric core, and it is LiPF that electric core is annotated electrolytic salt
6Normal temperature type electrolyte, process flexible packing lithium ion battery.Through changing into, behind the partial volume, in the safe scholar's extra-high-speed low-temperature test chamber of Nanjing, carry out 0 ℃ ,-5 ℃ ,-10 ℃ low-temperature tests respectively, it is following that test data low temperature discharge capacity accounts for the percentage of normal temperature discharge capacity:
| Probe temperature | 0℃ | -5℃ | -10℃ |
| Low temperature/normal temperature discharge capacity | 96.29％ | 91.32％ | 79.05％ |
Embodiment 3
With positive active material LiMn
2O
4, conductive agent CNT, binding agent LA133 be by 91: 5: 4 mixed; Negative electrode active material native graphite, conductive agent CNT, binding agent LA133 press 93: 3: 4 mixed; Technical process in 1 is processed electric core, and it is LiPF that electric core is annotated electrolytic salt
6Normal temperature type electrolyte, process flexible packing lithium ion battery.Through changing into, behind the partial volume, in the safe scholar's extra-high-speed low-temperature test chamber of Nanjing, carry out 0 ℃ ,-5 ℃ ,-10 ℃ low-temperature tests respectively, it is following that test data low temperature discharge capacity accounts for the percentage of normal temperature discharge capacity:
| Probe temperature | 0℃ | -5℃ | -10℃ |
| Low temperature/normal temperature discharge capacity | 95.92％ | 90.82％ | 77.35％ |
Embodiment 4
With positive active material LiMn
2O
4, conductive agent SP, binding agent LA133 be by 93.5: 3.5: 3 mixed; Negative electrode active material native graphite, conductive agent SP, binding agent LA133 press 94.5: 2.5: 3 mixed; Technical process in 1 is processed electric core, and it is LiPF that electric core is annotated electrolytic salt
6Normal temperature type electrolyte, process flexible packing lithium ion battery.Through changing into, behind the partial volume, in the safe scholar's extra-high-speed low-temperature test chamber of Nanjing, carry out 0 ℃ ,-5 ℃ ,-10 ℃ low-temperature tests respectively, it is following that test data low temperature discharge capacity accounts for the percentage of normal temperature discharge capacity:
| Probe temperature | 0℃ | -5℃ | -10℃ |
| Low temperature/normal temperature discharge capacity | 69.29％ | 60.38％ | 6.91％ |
Embodiment 5
With positive active material LiMn
2O
4, conductive agent SP, binding agent LA133 be by 93.5: 3.5: 3 mixed; Negative electrode active material native graphite, conductive agent SP, binding agent LA133 press 94.5: 2.5: 3 mixed; Technical process in 1 is processed electric core; The electricity core is annotated the low temperature electrolytic solution that is added with vinylene carbonate, gamma-butyrolacton additive, processes flexible packing lithium ion battery.Through changing into, behind the partial volume, in the safe scholar's extra-high-speed low-temperature test chamber of Nanjing, carry out 0 ℃ ,-5 ℃ ,-10 ℃ low-temperature tests respectively, it is following that test data low temperature discharge capacity accounts for the percentage of normal temperature discharge capacity:
| Probe temperature | 0℃ | -5℃ | -10℃ |
| Low temperature/normal temperature discharge capacity | 94.01％ | 91.26％ | 85.89％ |
Embodiment 6
With positive active material LiMn
2O
4, conductive agent CNT, binding agent LA133 be by 91: 5: 4 mixed; Negative electrode active material native graphite, conductive agent CNT, binding agent LA133 press 93: 3: 4 mixed; Technical process in 1 is processed electric core; The electricity core is annotated the low temperature electrolytic solution that is added with vinylene carbonate, gamma-butyrolacton additive, processes flexible packing lithium ion battery.Through changing into, behind the partial volume, in the safe scholar's extra-high-speed low-temperature test chamber of Nanjing, carry out 0 ℃ ,-5 ℃ ,-10 ℃ low-temperature tests respectively, it is following that test data low temperature discharge capacity accounts for the percentage of normal temperature discharge capacity:
| Probe temperature | 0℃ | -5℃ | -10℃ |
| Low temperature/normal temperature discharge capacity | 96.92％ | 92.82％ | 87.35％ |
Data from above embodiment can be found out; Under 25～-5 ℃ low temperature environment; The present invention-a kind of method and data by MoM and MEI of improving power lithium-ion battery cryogenic property under different low temperature environments; Not only can reach the effect the same but also more economic, be more suitable for putting into production than additive method with additive method.
Claims (10)
1. a method of improving power lithium-ion battery cryogenic property under different low temperature environments is characterized in that changing its cryogenic property under different low temperature environments through changing the factor that influences the lithium ion battery cryogenic property.
2. mainly contain the diffusivity in conductive capability, electrode interface and the battery active material of lithium ion in electrolyte by the described factor that influences the lithium ion battery cryogenic property of claim 1.
3. mainly change through the kind that changes conductive agent by the diffusivity of lithium ion in electrode active material under the said low temperature of claim 2, the conductive capability of lithium ion in electrolyte mainly changes through the kind that changes electrolyte under the low temperature.
4. the kind by the said conductive agent of claim 3 is mainly graininess conductive agent and wire conductive agent, and the kind of electrolyte is mainly normal temperature electrolyte and low-temperature electrolyte.
5. be mainly carbon black, acetylene black and SP by the said graininess conductive agent of claim 4, the wire conductive agent is mainly carbon fiber and CNT, and normal temperature electrolyte is by electrolyte lithium salt LiClO
4, LiPF
6, LiBF
4, LiAsF
6, a kind of and organic solvent EC among the LiBOB, EMC, DEC, PC form, low-temperature electrolyte be add a kind of on the basis of normal temperature electrolyte or more than two kinds and two kinds additive form.
By the additive in the said electrolyte of claim 5 have that vinylene carbonate, gamma-butyrolacton, fluorinated ethylene carbonate, ethyl acetate, pyrimidine, fluorobenzene, propane sultone, lithium trifluoromethanesulp,onylimide, hexamethylene are basic, in the biphenyl one or more.
7. the kind by the said change conductive agent of claim 1 promptly changes the wire conductive agent into by original graininess conductive agent, and normal temperature electrolyte changes low-temperature electrolyte into
8. comprise the kind of conductive agent in the kind that changes conductive agent in the positive pole respectively, the negative pole by the kind of the described change conductive agent of claim 1 and change the kind of conductive agent in anodal, the negative pole simultaneously.
9. comprise positive active material LiCoO by the described electrode active material of claim 2
2, LiNiO
2, LiMn
2O
4, LiFePO
4, Li (Co
xNi
yMn
1-x-y) O
2(0＜x+y＜1) and mixture or alloy and negative electrode active material native graphite, modified graphite or Delanium.
10. be flexible packing lithium ion battery by the described lithium ion battery of claim 1; It is characterized by external packing is aluminum plastic film; Binding agent is an aqueous binders, mainly contains LA133, LA135, LA134, F105, F109, F133, F132, CMC, SBR, and solvent is a ultra-pure water.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105006593A (en) * | 2014-04-21 | 2015-10-28 | 宁德时代新能源科技有限公司 | Lithium ion secondary battery and electrolyte thereof |
| CN106207092A (en) * | 2016-09-20 | 2016-12-07 | 广东国光电子有限公司 | A kind of combined anode slice of lithium ion battery of conductive agent and preparation method thereof |
| CN108063230A (en) * | 2017-12-14 | 2018-05-22 | 成都新柯力化工科技有限公司 | A kind of low temperature lithium battery is modified fluorosulfuric acid iron lithium anode material and preparation method thereof |
| CN108987687A (en) * | 2018-06-22 | 2018-12-11 | 中南大学 | A kind of low-temperature lithium ion battery graphite cathode material and preparation method thereof |
| CN116885197A (en) * | 2023-09-07 | 2023-10-13 | 四川易纳能新能源科技有限公司 | Positive electrode plate, preparation method thereof and sodium ion battery |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1790800A (en) * | 2004-12-14 | 2006-06-21 | 中国电子科技集团公司第十八研究所 | Lithium ion battery capable of low-temperature working |
-
2011
- 2011-09-30 CN CN2011102938713A patent/CN102340006A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1790800A (en) * | 2004-12-14 | 2006-06-21 | 中国电子科技集团公司第十八研究所 | Lithium ion battery capable of low-temperature working |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105006593A (en) * | 2014-04-21 | 2015-10-28 | 宁德时代新能源科技有限公司 | Lithium ion secondary battery and electrolyte thereof |
| CN105006593B (en) * | 2014-04-21 | 2017-12-12 | 宁德时代新能源科技股份有限公司 | Lithium ion secondary battery and electrolyte thereof |
| CN106207092A (en) * | 2016-09-20 | 2016-12-07 | 广东国光电子有限公司 | A kind of combined anode slice of lithium ion battery of conductive agent and preparation method thereof |
| CN108063230A (en) * | 2017-12-14 | 2018-05-22 | 成都新柯力化工科技有限公司 | A kind of low temperature lithium battery is modified fluorosulfuric acid iron lithium anode material and preparation method thereof |
| CN108987687A (en) * | 2018-06-22 | 2018-12-11 | 中南大学 | A kind of low-temperature lithium ion battery graphite cathode material and preparation method thereof |
| CN108987687B (en) * | 2018-06-22 | 2021-04-27 | 中南大学 | Low-temperature lithium ion battery graphite negative electrode material and preparation method thereof |
| CN116885197A (en) * | 2023-09-07 | 2023-10-13 | 四川易纳能新能源科技有限公司 | Positive electrode plate, preparation method thereof and sodium ion battery |
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Application publication date: 20120201 |