CN1805180A - Preparation method of positive electrode material of lithium ion secondary cell - Google Patents
Preparation method of positive electrode material of lithium ion secondary cell Download PDFInfo
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- CN1805180A CN1805180A CNA2005100096202A CN200510009620A CN1805180A CN 1805180 A CN1805180 A CN 1805180A CN A2005100096202 A CNA2005100096202 A CN A2005100096202A CN 200510009620 A CN200510009620 A CN 200510009620A CN 1805180 A CN1805180 A CN 1805180A
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- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to a method for preparing the lithium secondary battery anode material. The inventive material comprises any two or three of lithium cobalt oxide, lithium nickel oxide, and lithium manganese oxide to be mixed, to be baked for 8-16 hours in 700-1000Deg. C and milled into black powder, while the diameter ranges from 5-25um. The inventive composite material can form stable mixed crystal structure with stable crystal lattice. The lithium battery with said invention can improve the capacity, cycle service life and over-charge safety of lithium secondary battery.
Description
[technical field]: the present invention relates to a kind of preparation method of lithium ion secondary battery anode material, and the lithium rechargeable battery by using the synthetic positive electrode of this method to make.
[background technology]: lithium rechargeable battery, because it has characteristics such as high-energy-density, high working voltage, high power characteristic and stable discharge platform, quick charge characteristic, long cycle life, safety non-pollution, and used widely.Along with the fast development of mobile phone, notebook computer, digital product, the demand of lithium ion battery is increased day by day, just more and more important to the research of lithium ion secondary battery anode material accordingly.The employed material of lithium ion secondary battery positive electrode has lithium cobalt oxygen, lithium nickel oxygen and lithium manganese oxygen, and three kinds of materials respectively have pluses and minuses, and wherein being used maximum is lithium cobalt oxygen, stable performance, easily synthetic, but because its price comparison height, add resource-constrained, be necessary to develop other positive electrode.If use single lithium manganese oxygen positive electrode, though price is low, resource is wide,, the energy density of lithium manganese oxygen is littler than lithium cobalt oxygen, can dissolve gradually in electrolyte and capacity attenuation takes place; In the deep discharge process Jahn-Teller distortion can take place, the electrode activity composition is lost.And poor stability under cycle performance difference and the hot conditions; And use the positive electrode of lithium nickel oxygen separately, and though the capacity of battery is improved, self-discharge rate is low, does not have environmental pollution, and is lower to the requirement of electrolyte, the synthesis condition of lithium nickel oxygen is very harsh, easily generates the nickel of other valence state.And materials such as LiFePO 4 also can't be used at present owing to the respond difference.Above reason has caused the independent use of above-mentioned material that limitation is respectively arranged, and table 1 is common positive electrode characteristics contrast table.
The positive electrode characteristics contrast table that table 1 is common
| Positive electrode | Advantage | Shortcoming |
| Lithium cobalt oxygen (LiCoO 2) | Specific capacity higher (138mAh/g) but the good cycle high current charge-discharge | Resource-constrained price high security is poor |
| Lithium nickel oxygen (LiNiO 2) | Specific capacity the highest (180mAh/g) price is lower | The relatively poor production control difficulty of cycle performance poor stability |
| Spinel lithium manganese oxide (LiMn 2O 2) | It is good low in the pollution of the environment that the price low-resource enriches the good fail safe of high rate during charging-discharging | Low (100～110mAh/g) the high temperature decay fast (50～60 degree) of specific capacity |
| Layered LiMnO (LiMn 1-xM XO 2) | It is good low in the pollution of the environment that the price low-resource enriches fail safe | High rate during charging-discharging difference cycle performance has structural instability to be solved |
| LiFePO 4 (LiFePO 4) | It is good low in the pollution of the environment that the price low-resource enriches fail safe | The low interface of high rate during charging-discharging difference tap density reacting dynamics condition is poor, wouldn't the tool application conditions |
How to bring into play the advantage of various materials, overcome its shortcoming, it is the research focus of lithium ion secondary battery anode material always, using composite material is one of method of the most normal use, cobalt acid lithium, lithium nickelate and LiMn2O4 are carried out doping vario-property, change its crystallization and electronic structure, improve its various performances.Following patent has been introduced the preparation method of several composite positive poles respectively.
The positive electrode of patent 00117347.2 (anode material for lithium-ion batteries and preparation method thereof) is the cobalt acid lithium that the parcel layer of even has layered crystal structure on the surface of LiMn2O4, its preparation method comprises that solubility lithium salts, solubility cobalt salt are made into the aqueous solution earlier, mix, disperse to form suspension system through ultrasonic wave, make the solution that contains modifier form complete wetting on the lithium manganate particle surface, the preparation powder, anode material for lithium-ion batteries after heat treatment.
The preparation method of the positive electrode of patent 99113982.8 (positive electrode active materials and manufacture method and the purposes that are used for lithium rechargeable battery) mixes a certain proportion of lithium-containing compound, cobalt compound and nickel compound containing and grinding, mixture is molded into cellular block of material, afterwards again with piece material sintering in oxygen-containing atmosphere.Make positive electrode.
The method for preparing anode material of patent 97198469.7 (lithium/nickel/cobalt composite oxide and method for making thereof and the active material of positive electrode that is used for storage battery) is lithium-nickel-cobalt-oxygen thing (Li
yNi
1-xCo
X1M
X2O
2) in M be selected from any ratio on request among Al, Fe, Mn and the B, the lithium compound of amount on request joins in a kind of alkali metal salt and forms slurry, with formed slurry spray drying or freeze drying and in oxygen atmosphere, be about under 600～900 ℃ spray drying or the heating of cryodesiccated product 4 hours in temperature.
The preparation method of the positive electrode of patent 02128853.4 (a kind of method for preparing ball-shaped lithium-ion battery anode material) is with the solubility cobalt salt, manganese salt or nickel salt and solubility lithium salts wiring solution-forming, with this solution spray drying, 300～450 ℃ of inlet temperatures, 200～350 ℃ of outlet temperatures, obtain the precursor powder, then this precursor powder is carried out thermal decomposition in thermal decomposition furnace, 850～1000 ℃ of control temperature, cyclonic separation is collected powder, at last this powder was calcined 5～25 hours down at 750～800 ℃ under stirring, obtained ball-shaped lithium-ion battery anode material.
[content of the present invention]: the object of the present invention is to provide a kind of anode material of lithium cobalt oxygen, lithium nickel oxygen, the lithium manganese oxygen preparation process of mixture that can improve lithium ion secondary battery capacity, circulation and high-temperature behavior, the present invention is in order to solve the problem of existence, reduce the content of above-mentioned said cobalt acid lithium, thereby reduce cost, energy savings, improve the capacity of battery, improve the fail safe of battery, make battery have excellent cycle performance.The preparation method of positive electrode of the present invention just any two materials in lithium cobalt oxygen, lithium manganese oxygen and the lithium nickel oxygen or three kinds of materials on request ratio carry out ground and mixed, carry out 700～1000 ℃ roasting after mixing, time is 8～16 hours, get the positive electrode of particle size distribution at 5～25 μ m after grinding the screening cooling, manufacture craft is fairly simple.
The invention will be further described below in conjunction with embodiment and accompanying drawing:
Embodiment 1:
The mixture that takes by weighing an amount of lithium cobalt oxygen and lithium nickel oxygen carries out ground and mixed, and the ratio of taking by weighing is a lithium cobalt oxygen: lithium nickel oxygen=2: 1; Carry out high-temperature roasting after grinding and handled 8～16 hours under oxygen atmosphere, temperature is 700～1000 ℃, take out after the cooling positive electrode.Make conductive agent with acetylene black, Kynoar is a binding agent, and n-formyl sarcolysine base pyrrolidones (NMP) is a solvent, fully mixes and makes slurry.It consists of positive electrode: acetylene black: PVDF=95: 2.0: 3.0.This slurry is coated on equably on the aluminium foil of 15～20 μ m, in 120 ℃ of dryings.Obtain the positive plate that thickness is about 125 μ m after the calendering, positive and negative intermittently are coated with, and reserve the uncoated metal of certain intervals; Negative pole uses a kind of carbon materials that can make lithium ion embed and take off embedding repeatedly, and this carbon materials comprises native graphite, coating decoration native graphite, Delanium, MCMB, MCF, VGCF etc.; Positive and negative electrode pole piece and polyethylene micropore barrier film are reeled; Electrolyte with an organic solvent comprises chain acid esters (, sulfur-bearing fluorine-containing as DMC, DEC, EMC, MPC, DPC, MA, EA, PA, dimethoxy-ethane, diethoxyethane and other or contain the chain organosilane ester of unsaturated bond) and ring-type acid esters (, sulfur-bearing fluorine-containing as EC, PC, VC, CHB, γ-BL, sultone and other or contain the ring-type organosilane ester of unsaturated bond), can use one of them or several mixing.Inorganic salts comprise: LiCLO
4, LiPF
6, LiBF
4, LiAsF
6, trifluoromethyl sulfonic acid lithium LiBOB etc.; Change into after injecting electrolyte, charging current is 0.2C
5, charging is carried out constant current charge-discharge circulation 100 times, charging and discharging currents 0.2～1.0C afterwards by voltage 3.9V
5, discharge and recharge by voltage 4.20～3.0V, the battery of first charge-discharge, test result calculations show battery that this material makes first specific capacity be 150mAh/g, the result can improve the capacity of battery.Test result is seen Figure of description 1.
Embodiment 2:
The mixture that takes by weighing an amount of lithium nickel oxygen, lithium manganese oxygen and lithium cobalt oxygen carries out ground and mixed, and the ratio of taking by weighing is a lithium nickel oxygen: lithium manganese oxygen: lithium cobalt oxygen=2: 2: 4; Carry out high-temperature roasting after grinding and handled 8～16 hours under oxygen atmosphere, temperature is 700～1000 ℃, take out after the cooling positive electrode.Other method is identical with embodiment 1, behind the battery, carry out capacity and security performance and detect, the result is 140mAh/g for specific capacity first, by measuring 100 capacity attenuations of circulation, gets the cycle performance that the result can improve battery, test result is seen Figure of description 2.
Embodiment 3:
The mixture that takes by weighing an amount of lithium cobalt oxygen and lithium manganese oxygen carries out ground and mixed, and the ratio of taking by weighing is a lithium cobalt oxygen: lithium manganese oxygen=2: 1; Carry out high-temperature roasting after grinding and handled 8～16 hours under oxygen atmosphere, temperature is 700～1000 ℃, take out after the cooling positive electrode.Other method is identical with embodiment 1, behind the battery, carry out security performance and detect, the results are shown in Table 2.
Comparative example 1:
Take by weighing an amount of lithium cobalt oxygen as positive electrode, other method is identical with embodiment 1, behind the battery, carry out capacity check, the result is 140mAh/g for specific capacity first, the capacity that circulates 100 times carries out the security performance detection, the results are shown in accompanying drawing and table 2.
Specifically relatively see Table 2 and accompanying drawing:
Table 2 security performance testing result table
| Battery status | Pilot project | Test method | Test standard | Result of the test |
| Embodiment 3 | The high magnification over-charging | Get 10 batteries with electric current 1C 5After the A discharge, with 3C 5The A current charges is to 10V, transfer constant voltage charge then to cut-off current (20mA) or 8 hours, record failure mode and inefficacy time of origin. | Do not break, do not explode, not on fire, surface temperature is the highest is no more than 150 | 10 all qualified |
| Comparative example 1 | The high magnification over-charging | Get 20 batteries, with electric current 1C 5After the A discharge, with 3C 5The A current charges is to 4.8V (10) and 10V (10), transfer constant voltage charge then to cut-off current (20mA) or 8 hours, record failure mode and inefficacy time of origin. | Do not break, do not explode, not on fire, surface temperature is the highest is no more than 150 ℃ | 4 battery explosions in the battery of qualified 10 10V of the battery of 10 4.8V |
The figure explanation:
Fig. 1: lithium cobalt oxygen and lithium nickel oxygen mixed sintering and lithium oxygen plus plate material make the battery cycle life correlation curve
Fig. 2: lithium cobalt oxygen and lithium cobalt oxygen, lithium nickel oxygen and lithium manganese oxygen mixed sintering positive electrode make the battery cycle life correlation curve
Claims (6)
1, a kind of preparation method of lithium ion secondary battery anode material: it is characterized in that with wantonly two kinds or three kinds of materials mixing in lithium cobalt oxygen, lithium nickel oxygen, the lithium manganese oxygen, form its mixture, and then with roasting under 700～1000 ℃ of temperature oxygen atmospheres 8～16 hours, take out the cooling back, sieve the positive electrode that gets product through grinding, the particle size distribution of material is at 5～25 μ m.
2, according to claim 1, it is characterized in that three kinds of lithium salts that exist are the positive electrode of commercially available lithium rechargeable battery.
3, according to claim 1, it is characterized in that wantonly two kinds or three kinds in lithium cobalt oxygen, lithium nickel oxygen, the lithium manganese oxygen are evenly mixed, the ratio of each lithium salts wherein is no more than 50% with the ratio of lithium nickel oxygen and is as the criterion, and other ratio is determined according to capacity and security requirement.
4, utilize 1,2,3 lithium rechargeable batteries that prepared material makes for positive active material of right, it is characterized in that: negative pole corresponding with it contains a kind of carbon materials that can make lithium ion embed and take off embedding repeatedly, and this carbon materials comprises native graphite, coating decoration native graphite, Delanium, MCMB, MCF, VGCF etc.
5, according to claim 1,2,3 prepared materials are the lithium rechargeable battery that positive active material makes, it is characterized in that: used in battery electrolyte is made up of organic solvent and inorganic salts, organic solvent comprises that the chain acid esters is (as DMC, DEC, EMC, MPC, DPC, MA, EA, PA, dimethoxy-ethane, diethoxyethane and other are fluorine-containing, sulfur-bearing or contain the chain organosilane ester of unsaturated bond) and the ring-type acid esters (as EC, PC, VC, CHB, γ-BL, sultone and other are fluorine-containing, sulfur-bearing or contain the ring-type organosilane ester of unsaturated bond), can use one of them or several mixing.Inorganic salts comprise: LiCLO
4, LiPF
6, LiBF
4, LiAsF
6, trifluoromethyl sulfonic acid lithium LiBOB etc.
6, according to the lithium rechargeable battery of claim 4, it is characterized in that: battery case is a metallic aluminium, stainless steel or stainless steel nickel plating, and battery case can also be the plastic-aluminum flexible packing film.The battery case shape can be cube type or column type.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101901932A (en) * | 2010-05-17 | 2010-12-01 | 江西省福斯特新能源有限公司 | Quick-chargeable, high-security and high-multiplying-power battery and production method thereof |
| CN103782422A (en) * | 2011-09-19 | 2014-05-07 | 巴斯夫欧洲公司 | Tin oxide-containing polymer composite materials |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1173966A (en) * | 1997-07-01 | 1999-03-16 | Matsushita Electric Ind Co Ltd | Nonaqueous electrolyte secondary battery and manufacture of its positive electrode active material |
| JP3355126B2 (en) * | 1998-01-30 | 2002-12-09 | 同和鉱業株式会社 | Positive electrode active material for lithium ion secondary battery, method for producing the same, and lithium ion secondary battery |
| CN1373528A (en) * | 2001-03-06 | 2002-10-09 | 中国科学院成都有机化学研究所 | Postive electrode material of li-ion accumulator and its preparing process |
| CN1172387C (en) * | 2002-08-16 | 2004-10-20 | 中国科学院理化技术研究所 | Method for preparing spherical positive pole active material for lithium ion position |
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2005
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101901932A (en) * | 2010-05-17 | 2010-12-01 | 江西省福斯特新能源有限公司 | Quick-chargeable, high-security and high-multiplying-power battery and production method thereof |
| CN101901932B (en) * | 2010-05-17 | 2015-07-08 | 江西省福斯特新能源有限公司 | Quick-chargeable, high-security and high-multiplying-power battery and production method thereof |
| CN103782422A (en) * | 2011-09-19 | 2014-05-07 | 巴斯夫欧洲公司 | Tin oxide-containing polymer composite materials |
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Owner name: ZHUHAI GUANGYU BATTERY CO., LTD. Free format text: FORMER OWNER: HARBIN GUANGYU POWER CO., LTD. Effective date: 20090925 |
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Effective date of registration: 20090925 Address after: No. 209 Guangdong Province, Zhuhai city Doumen District Xinqing Science and Technology Industrial Park, Mount Everest Boulevard Patentee after: ZHUHAI COSLIGHT BATTERY Co.,Ltd. Address before: No. 8 South Street, Yingbin Road, Harbin Development Zone, Harbin, Heilongjiang, Taihu Patentee before: HARBIN COSLIGHT POWER Co.,Ltd. |
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Address after: 209 No. 519180 Guangdong province Zhuhai city Doumen District Xinqing Science and Technology Industrial Park, Mount Everest Boulevard Patentee after: Zhuhai Guanyu Battery Co.,Ltd. Address before: 209 No. 519180 Guangdong province Zhuhai city Doumen District Xinqing Science and Technology Industrial Park, Mount Everest Boulevard Patentee before: ZHUHAI COSLIGHT BATTERY Co.,Ltd. Address after: 209 No. 519180 Guangdong province Zhuhai city Doumen District Xinqing Science and Technology Industrial Park, Mount Everest Boulevard Patentee after: ZHUHAI COSLIGHT BATTERY Co.,Ltd. Address before: 209 No. 519180 Guangdong province Zhuhai city Doumen District Xinqing Science and Technology Industrial Park, Mount Everest Boulevard Patentee before: ZHUHAI COSLIGHT BATTERY Co.,Ltd. |
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