CN102074731B - Manganese, nickel and titanium lithium ion battery and preparation method thereof - Google Patents
Manganese, nickel and titanium lithium ion battery and preparation method thereof Download PDFInfo
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- CN102074731B CN102074731B CN201010582333.1A CN201010582333A CN102074731B CN 102074731 B CN102074731 B CN 102074731B CN 201010582333 A CN201010582333 A CN 201010582333A CN 102074731 B CN102074731 B CN 102074731B
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- Y02E60/10—Energy storage using batteries
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Abstract
The invention relates to a lithium ion battery mainly taking manganese, nickel and titanium as anode and cathode materials and aluminum foils as anode and cathode collectors, and a preparation method thereof. In the manganese, nickel and titanium lithium ion battery, a cathode consists of lithium manganate, a ternary composite material, other solid mixtures of the cathode, and a cathode solvent; and the anode consists of nano lithium titanate, other solid mixtures of the anode, and an anode solvent. Compared with the prior art, the novel lithium ion battery has the advantages of strategically long service life, good electrical property, low cost, safety and environmental friendliness; and the prepared batteries are soft package and steel shell lithium ion batteries and polymer lithium ion batteries.
Description
Technical field
The present invention relates to a kind of is mainly both positive and negative polarity raw material with manganese, nickel, titanium, lithium-ion-power cell that the aluminium foil of take is both positive and negative polarity collector and preparation method thereof, lithium-ion-power cell particularly a kind ofly have extended cycle life, high temperature performance being good, safe and reliable, production cost is low and preparation method thereof.
Background technology
The energy and environment are that human society is depended on for existence and development and very important material base.Countries in the world, after being successively based upon energy system on the fossil fuel bases such as oil, coal and natural gas and forming, have greatly promoted prosperity, progress and the development of human society.But, along with world suffers from the bitter lesson of the various unfortunate disaster facts and improving constantly of human sciences's predictive ability, whole world villager more and more feels and is being faced with severe awkward predicament in its forward march: non-renewable fossil fuel will be petered out, and the storm of energy crisis grows in intensity; A large amount of exploitations and the use of fossil fuel, severe contamination and the ecological destruction of having caused environment.Therefore, countries in the world are found the Strategic Measure of energy security one after another, Devoting Major Efforts To Developing is with diversification energy systems such as solar energy, wind energy, water power, nuclear powers, and extremely pay attention to development and take the electric automobile that lithium ion battery is power plant module, employing with electricity for oil, reduce the discharge of carbon dioxide, can store again the low electric paddy of electrical network, be the income that obtains killing three birds with one stone simultaneously.
Relevant ministries and commissions of country point out recently; China will reach 200,000,000 to the recoverable amount of the year two thousand twenty domestic automobile; to there is serious crisis in energy security and environmental pollution when the time comes, therefore, the energy-saving and emission-reduction of traditional fuel-engined vehicle and the industrialization of new-energy automobile just become important topic urgently to be resolved hurrily.
< < electric automobile development in science and technology " 12 " the ad hoc planning > > being taken the lead by the Ministry of Science and Technology has in the recent period formulated complete.According to this planning, miniaturization and automobile electric gasification are two general orientation of Chinese automobile future development, and Electric Cars in China recoverable amount in 2015 plan reaches 1,000,000.In addition, by national Ministry of Industry and Information, taken the lead that the < < that formulates is energy-conservation to be completed with new-energy automobile development plan > >.Planning accordingly, 10 years from now on, will drop into 1,000 hundred million support funds, domesticly will add up direct increase and invest 5 trillion yuan ....The year two thousand twenty New Energy Sources In China sale of automobile target scale may be the whole world first.
The new breakthrough of lithium-ion-power cell has made the production cost of pure electric automobile greatly reduce, and performance is greatly improved, and the marketization is close at hand.Promote with the least delay possible the industrialization of lithium-ion-power cell, driving New-energy electric vehicle industrialization is the strategic choice tallying with the national condition.Promote pure electric automobile and be China's rare historic opportunities in fierce international competition.Industrialization Jiang Shi China of lithium-ion-power cell likely realizes great-leap-forward development accordingly in global New Energy Industry, and takes its place in the front ranks of the world, and may become " electric automobile kingdom ".
At present, domestic and international most units manufacture in the process of lithium-ion-power cell in research and development, still use the negative material that electrographite is electrokinetic cell.But, manufacture the raw material of electrographite and will use stone tar, after oil exhaustion, stone tar has not just had yet, and when the time comes, the negative material electrographite of electrokinetic cell is also just unsustainable.
Summary of the invention
In order to overcome the deficiencies in the prior art, the present invention is with LiMn2O4 (LiMn
2o
4) add ternary (LiNixCoyMnz) composite material for anodal, with nano lithium titanate (Li4Ti
5o
12) be negative pole, aluminium foil is the lithium-ion-power cell of both positive and negative polarity collector, in its raw materials for production, the compound of lithium metal, titanium, manganese, nickel and metallic aluminium ， China are very abundant, have clear superiority.Particularly the having extended cycle life of manganese, the nickel of our invention, titanium based lithium-ion electrokinetic cell, high temperature performance wide ranges, safe and reliable, production cost is low, for very wide prospect has been created in the extensive use of lithium-ion-power cell.
The object of the invention is to realize by following technical solution: manganese of the present invention, nickel, titanium based lithium-ion electrokinetic cell, anode formula is by LiMn2O4, trielement composite material, anodal other solid mixture, anodal solvent composition, wherein: described trielement composite material is comprised of Ni, Co, Mn, other solid mixture of described positive pole is comprised of SP, S-O, PVDF, described anodal solvent is that NMP forms, described LiMn2O4: described trielement composite material=(70%～100%): (30%～0%); The component of described trielement composite material is: Ni: Co: Mn=[(10/3)～5]: [2～(10/3)]: [3～4], described anodal solid mixture: NMP=(64～66): (36～34); Cathode formula is by nano lithium titanate, other solid mixture of negative pole, negative pole solvent composition, wherein: other solid mixture of described negative pole is comprised of SP, PVDF, described negative pole solvent is that NMP forms, described negative pole solid mixture: NMP=(0.9～1.1): (1.1～0.9).
The present invention can also be comprised of carbon black, PVDF, DBP by other solid mixture of described positive pole, and described anodal solvent is acetone, described anodal solid mixture: acetone=(34～36): (66～64); Other solid mixture of described negative pole is comprised of SP, DBP; Described negative pole solvent is acetone, wherein: described negative pole solid mixture: acetone=(44～46): (56～54).
Manganese of the present invention, nickel, titanium based lithium-ion electrokinetic cell, is characterized in that the component of described trielement composite material is: Ni: Co: Mn=4: 2: 4.
In manganese of the present invention, nickel, titanium based lithium-ion electrokinetic cell, the component of described trielement composite material can also be: Ni: Co: Mn=5: 2: 3.
In manganese of the present invention, nickel, titanium based lithium-ion electrokinetic cell, the component of described trielement composite material can be also: Ni: Co: Mn=(1/3): (1/3): (1/3).
The preparation method of manganese of the present invention, nickel, titanium based lithium-ion electrokinetic cell, described battery changes into flow process and parameter is as follows:
1) shelve 3 minutes;
2) with 0.01CA constant current charge 150 minutes, upper voltage limit 2.5v;
3) with 0.02CA constant current charge 200 minutes, upper voltage limit 2.5v;
4) with 0.05CA constant current charge 150 minutes, upper voltage limit 2.5v;
5) shelve 3 minutes;
6) with 0.1CA constant current charge 150 minutes, upper voltage limit 2.5v;
7) with 0.2CA constant current charge 120 minutes, upper voltage limit 2.5v;
8) with 0.5CA constant-current constant-voltage charging 180 minutes, upper voltage limit 2.5v; Cut-off current
0.01CA；
9) shelve 15 minutes;
10) with 0.5CA constant-current discharge to final voltage 1.5v;
11) shelve 15 minutes;
12) with 0.5CA constant-current constant-voltage charging 90 minutes, upper voltage limit 2.5v, cut-off current 0.01CA.
The preparation method of manganese of the present invention, nickel, titanium based lithium-ion electrokinetic cell, is characterized in that described battery partial volume flow process and parameter are as follows:
1) shelve 3 minutes
2) with 0.5CA constant-current constant-voltage charging 180 minutes, upper voltage limit 2.5v, cut-off current 0.01CA
3) shelve 15 minutes
4) with 0.5CA constant-current discharge to final voltage 1.5v;
5) shelve 15 minutes
6) with 0.5C constant-current constant-voltage charging 90 minutes, upper voltage limit 2.5v, cut-off current 0.01CA.
Compared with prior art, the life-span with strategic importance is grown, electrically excellent, cost is low, the new type lithium ion electrokinetic cell of safety and environmental protection in the present invention, and its battery types of preparing is divided into: Soft Roll and box hat lithium-ion-power cell and polymer lithium ion power cell.
Accompanying drawing explanation
Fig. 1 is the process chart that method for soft package lithium ion power of the present invention is made.
Fig. 2 is box hat lithium-ion-power cell fabrication processing figure of the present invention.
Fig. 3 is polymer lithium ion power cell fabrication processing figure of the present invention.
Embodiment
The formula of anode and cathode slurry of the present invention and relevant parameter:
1, Soft Roll and box hat battery:
Anode formula: LiMn2O4, trielement composite material, SP, S-O, PVDF; Solvent is NMP.
Cathode formula: nano lithium titanate, SP, PVDF, solvent are NMP.
Embodiment 1
LiMn2O4: trielement composite material=70%: 30%; The component of trielement composite material is: Ni: Co: Mn=4: 2: 4.
Anodal solid mixture: NMP=64: 36
Negative pole solid mixture: NMP=0.9: 1.1
Embodiment 2
LiMn2O4: trielement composite material=80%: 20%; The component of trielement composite material is: Ni: Co: Mn=5: 2: 3.
Anodal solid mixture: NMP=65: 35
Negative pole solid mixture: NMP=1: 1
Embodiment 3
LiMn2O4: trielement composite material=100%: 0%; The component of trielement composite material is: Ni: Co: Mn=1/3: 1/3: 1/3.
Anodal solid mixture: NMP=66: 34
Negative pole solid mixture: NMP=1.1: 0.9
2, polymer battery
Anode formula: LiMn2O4, trielement composite material, carbon black, PVDF, DBP; Solvent is acetone.
Wherein:
The proportioning of LiMn2O4 to trielement composite material, the component of trielement composite material and Soft Roll, box hat battery are identical.
Cathode formula: nano lithium titanate, SP, DBP; Solvent is acetone.
Embodiment 1
Anodal solid mixture: acetone=34: 66
Negative pole solid mixture: acetone=44: 56
Embodiment 2
Anodal solid mixture: acetone=35: 65
Negative pole solid mixture: acetone=45: 55
Embodiment 3
Anodal solid mixture: acetone=36: 64
Negative pole solid mixture: acetone=46: 54
In the present invention, Fig. 1 is the process chart that method for soft package lithium ion power of the present invention is made.Fig. 2 is box hat lithium-ion-power cell fabrication processing figure of the present invention.Fig. 3 is polymer lithium ion power cell fabrication processing figure of the present invention.
Battery forming and capacity dividing flow process of the present invention and parameter are as follows:
(1) change into:
1, shelve 3 minutes;
2, with 0.01CA constant current charge 150 minutes, upper voltage limit 2.5v;
3, with 0.02CA constant current charge 200 minutes, upper voltage limit 2.5v;
4, with 0.05CA constant current charge 150 minutes, upper voltage limit 2.5v;
5, shelve 3 minutes;
6, with 0.1CA constant current charge 150 minutes, upper voltage limit 2.5v;
7, with 0.2CA constant current charge 120 minutes, upper voltage limit 2.5v;
8, with 0.5CA constant-current constant-voltage charging 180 minutes, upper voltage limit 2.5v; Cut-off current 0.01CA;
9, shelve 15 minutes;
10, with 0.5CA constant-current discharge to final voltage 1.5v;
11, shelve 15 minutes;
12, with 0.5CA constant-current constant-voltage charging 90 minutes, upper voltage limit 2.5v, cut-off current 0.01CA
(2) partial volume:
1, shelve 3 minutes
2, with 0.5CA constant-current constant-voltage charging 180 minutes, upper voltage limit 2.5v, cut-off current 0.01CA
3, shelve 15 minutes
4, with 0.5CA constant-current discharge to final voltage 1.5v;
5, shelve 15 minutes
6, with 0.5C constant-current constant-voltage charging 90 minutes, upper voltage limit 2.5v, cut-off current 0.01CA.
Although feature of the present invention and advantage thereof have been described a lot; yet be understandable that; for the person of ordinary skill of the art; can make other a variety of corresponding changes according to technical scheme of the present invention and technical though, and all these change the scope that all should belong to claim protection of the present invention.
Claims (5)
1. the preparation method of a manganese, nickel, titanium based lithium-ion electrokinetic cell, anode formula is by LiMn2O4, trielement composite material, anodal solid mixture, anodal solvent composition, wherein: described trielement composite material comprises Ni, Co, Mn, described anodal solid mixture is comprised of SP, S-O, PVDF, described anodal solvent is that NMP forms, described LiMn2O4: described trielement composite material=(70%～80%): (30%～20%); Ni in described trielement composite material, Co, Mn component are: Ni:Co:Mn=[(10/3)～5]: [2～(10/3)]: [3～4], described anodal solid mixture: NMP=(64～66): (36～34); Cathode formula is by nano lithium titanate, negative pole solid mixture, negative pole solvent composition, wherein: described negative pole solid mixture is comprised of SP, PVDF, described negative pole solvent is that NMP forms, described negative pole solid mixture: NMP=(0.9～1.1): (1.1～0.9);
It is characterized in that described battery changes into flow process and parameter is as follows:
1) shelve 3 minutes;
2) with 0.01CA constant current charge 150 minutes, upper voltage limit 2.5v;
3) with 0.02CA constant current charge 200 minutes, upper voltage limit 2.5v;
4) with 0.05CA constant current charge 150 minutes, upper voltage limit 2.5v;
5) shelve 3 minutes;
6) with 0.1CA constant current charge 150 minutes, upper voltage limit 2.5v;
7) with 0.2CA constant current charge 120 minutes, upper voltage limit 2.5v;
8) with 0.5CA constant-current constant-voltage charging 180 minutes, upper voltage limit 2.5v; Cut-off current 0.01CA;
9) shelve 15 minutes;
10) with 0.5CA constant-current discharge to final voltage 1.5v;
11) shelve 15 minutes;
12) with 0.5CA constant-current constant-voltage charging 90 minutes, upper voltage limit 2.5v, cut-off current 0.01CA;
Described battery partial volume flow process and parameter are as follows:
1) shelve 3 minutes
2) with 0.5CA constant-current constant-voltage charging 180 minutes, upper voltage limit 2.5v, cut-off current 0.01CA
3) shelve 15 minutes
4) with 0.5CA constant-current discharge to final voltage 1.5v;
5) shelve 15 minutes
6) with 0.5C constant-current constant-voltage charging 90 minutes, upper voltage limit 2.5v, cut-off current 0.01CA.
2. the preparation method of manganese according to claim 1, nickel, titanium based lithium-ion electrokinetic cell, it is characterized in that described anodal solid mixture is comprised of carbon black, PVDF, DBP, described anodal solvent is acetone, described anodal solid mixture: acetone=(34～36): (66～64); Described negative pole solid mixture is comprised of SP, DBP; Described negative pole solvent is acetone, wherein: described negative pole solid mixture: acetone=(44～46): (56～54).
3. the preparation method of manganese according to claim 1, nickel, titanium based lithium-ion electrokinetic cell, is characterized in that Ni, Co, the Mn ratio in described trielement composite material is: Ni:Co:Mn=4:2:4.
4. the preparation method of manganese according to claim 1, nickel, titanium based lithium-ion electrokinetic cell, is characterized in that Ni, Co, the Mn ratio in described trielement composite material is: Ni:Co:Mn=5:2:3.
5. the preparation method of manganese according to claim 1, nickel, titanium based lithium-ion electrokinetic cell, is characterized in that Ni, Co, the Mn ratio in described trielement composite material is: Ni:Co:Mn=(1/3): (1/3): (1/3).
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| CN102306730B (en) * | 2011-08-08 | 2013-09-04 | 能一郎科技股份有限公司 | Method for improving safety of high-capacity lithium ion power battery |
| CN106410170B (en) * | 2016-12-08 | 2018-11-09 | 深圳市鑫永丰科技有限公司 | Anode material for compound lithium ion battery and preparation method thereof and lithium ion battery |
| CN113140782B (en) * | 2021-05-27 | 2024-04-26 | 星恒电源股份有限公司 | High-performance low-cost lithium ion power battery and preparation method thereof |
Citations (4)
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| CN1529382A (en) * | 2003-10-04 | 2004-09-15 | 邓国友 | High-power plastic lithium-ion cell |
| CN1835262A (en) * | 2006-04-04 | 2006-09-20 | 北京中润恒动电池有限公司 | Anode active material compsns anode sheet and Li ion cell |
| CN101154747A (en) * | 2006-09-27 | 2008-04-02 | 比亚迪股份有限公司 | Formation method for lithium ion secondary battery |
| CN101425605A (en) * | 2007-11-01 | 2009-05-06 | 深圳市慧通天下科技股份有限公司 | Nickel-cobalt lithium manganate high power lithium ionic cell |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR100881637B1 (en) * | 2006-05-01 | 2009-02-04 | 주식회사 엘지화학 | Lithium Secondary Battery of Improved Low-Temperature Power Property |
| JP5319899B2 (en) * | 2007-08-23 | 2013-10-16 | 株式会社東芝 | Non-aqueous electrolyte battery |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1529382A (en) * | 2003-10-04 | 2004-09-15 | 邓国友 | High-power plastic lithium-ion cell |
| CN1835262A (en) * | 2006-04-04 | 2006-09-20 | 北京中润恒动电池有限公司 | Anode active material compsns anode sheet and Li ion cell |
| CN101154747A (en) * | 2006-09-27 | 2008-04-02 | 比亚迪股份有限公司 | Formation method for lithium ion secondary battery |
| CN101425605A (en) * | 2007-11-01 | 2009-05-06 | 深圳市慧通天下科技股份有限公司 | Nickel-cobalt lithium manganate high power lithium ionic cell |
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Inventor after: Ye Qing Inventor after: Lei Ruqing Inventor after: Wang Jianli Inventor after: Xia Hui Inventor before: Lei Ruqing Inventor before: Wang Siping Inventor before: Li Peng Inventor before: Dong Xiangsheng Inventor before: Xie Zhicheng |
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Effective date of registration: 20171010 Address after: 461500 Xuchang, Henan City, Changge Province on the eastern side of the Northern Wei Road Patentee after: Henan rotary Polytron Technologies Inc Address before: 437100 Hubei Xianning Economic Development Zone Changjiang Industrial Park Qinglong road can Lang Science Park Patentee before: Wewin Battery Technology Co., Ltd. |