CN101047245A - Method for preparing plus plate material of lithium ion battery by combustion method - Google Patents

Method for preparing plus plate material of lithium ion battery by combustion method Download PDF

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Publication number
CN101047245A
CN101047245A CNA2006101053088A CN200610105308A CN101047245A CN 101047245 A CN101047245 A CN 101047245A CN A2006101053088 A CNA2006101053088 A CN A2006101053088A CN 200610105308 A CN200610105308 A CN 200610105308A CN 101047245 A CN101047245 A CN 101047245A
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lithium
anode material
ion batteries
preparation
salt
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CN100483807C (en
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贾永忠
姚颖
景燕
孙进贺
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Qinghai Institute of Salt Lakes Research of CAS
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Qinghai Institute of Salt Lakes Research of CAS
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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
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    • Y02E60/10—Energy storage using batteries

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Abstract

A method for preparing positive electrode material of lithium cell by ignition includes mixing relevant transition metal with soluble salt material of lithium as per chemical metering ratio and dissolving mixed material by aqueous solution of nitric acid, adding certain amount of organic acid then agitating continuously under heating condition, making prepared material be quickly self-ignited under temperature of 600deg.c and baking self-ignited material under temperature of 600-800deg.c for 4-8 hours for obtaining positive electrode material of lithium cell.

Description

The method of method for preparing plus plate material of lithium ion battery by combustion
Technical field
The present invention relates to a kind of preparation of cell positive material, relate in particular to a kind of anode material for lithium-ion batteries and preparation method thereof.
Background technology
Lithium ion battery is meant with Li +Inserting compound is the secondary cell of both positive and negative polarity, is different from lithium battery and adopts lithium metal to make negative pole, and it has excellent charging and discharging reversibility and fail safe.Lithium ion battery operating voltage height, but energy density is big, security performance good, the little fast charging and discharging of self discharge, can make large-capacity battery pack, and is the memory-less effect battery.Along with modern electrical equipment microminiaturization, the needs of energetic, good power supply in light weight, that volume is little, high specific energy, high voltage, oligosaprobic lithium ion battery will become office, communication, computer, video camera and electric automobile etc.
Battery material is the main factor of restriction battery industry development.Stratiform and spinel-type lithium transition-metal oxide are considered to the preferential positive electrode of selecting of high energy density lithium ion battery.The production cost of seeking well behaved positive electrode and reduction electrode material is one of key issue of lithium ion battery development.
The method of synthetic positive electrode has solid phase method and liquid phase method.High temperature solid-state is synthetic be carbonate, nitrate, acetate, oxide or hydroxide etc. with lithium, transition metal as raw material, in air, be heated to 900 ℃ even higher temperature behind the mixed pressuring plate, need carry out long-time and the multistage heats.Low temperature solid phase synthesis rule is with raw material grinding for a long time in different atmosphere or organic solvent of lithium and transition metal, still needs in the uniform temperature long-time heating then.Liquid phase synthesizing method adopts sol-gal process more.The key of this method is to select suitable dispersant solution and the suitable pH value of control, and material is formed gel, removes organic substance and moisture content by the whole bag of tricks then, heats under higher temperature at last.
Different synthetic methods, the positive electrode chemical property that obtains differs greatly.Solid phase method energy consumption height, reactant mixes inhomogeneous, and the product pattern is irregular, the chemical property instability.The liquid phase rule is a complex process, and the reaction time is long, and the high production cost that makes of used organic solvent price is high.
Summary of the invention
The purpose of this invention is to provide a kind of anode material for lithium-ion batteries, but this material is made that operating voltage height, energy density behind the battery is big, security performance good, the little fast charging and discharging of self discharge, and can make large-capacity battery pack and memory-less effect.
Another object of the present invention provides a kind of a kind of preparation method of above-mentioned lithium ion cell positive: adopt liquid phase and solid phase combination, the reaction time is short, and production cost is low, and product purity height, uniform particles, stable electrochemical property.
Anode material for lithium-ion batteries of the present invention, its chemical formula is composed as follows:
Li[Co X?Mn Y?Ni (1-X-Y)]O 2
0≤X≤1,0≤Y≤1,0≤(X+Y)≤1 wherein;
Co, Mn, Ni can coexist or exist a kind ofly at least, and its amount of substance summation is 1 in chemical formula.
The anode material for lithium-ion batteries of the present invention's preparation is black-and-blue powder or black powder, is accredited as pure phase through X-ray diffraction, purity height, good stability.LiCoO 2, LiNiO 2, LiMnO 2Specific capacity can reach more than the 130mAh/g anode material for lithium-ion batteries LiCo 1/3Ni 1/3Mn 1/3O 2Discharge capacity reaches 148.13mAh/g, and the discharge capacity after the charge and discharge cycles 80 times is 132.39mAh/g, shows excellent electrochemical properties.Making operating voltage behind the battery is 3-5V, but energy density is big, security performance good, the little fast charging and discharging of self discharge, and can make large-capacity battery pack and memory-less effect.Charge and discharge efficient when experiment showed, generally speaking its charge and discharge cycles 20 times and still can reach 99.8～100%, show electrochemistry cycle performance preferably.
The preparation method of anode material for lithium-ion batteries of the present invention comprises following processing step:
1. lithium, transition metals cobalt, manganese, nickel salt are pressed 1: X: Y: (1-X-Y) amount of substance mixes, and dissolves fully with the aqueous solution of nitric acid of 1M, until obtaining homogeneous transparent solution; 0≤X≤1,0≤Y≤1,0≤(X+Y)≤1 wherein; Lithium, cobalt, manganese, nickel can coexist or exist a kind ofly at least, and its amount of substance summation is 1.
2. add organic acid in solution, the ratio of this organic acid addition and metal ion total amount (amount of substance) is 0.8: 1～2.0: 1;
3. under constantly stirring, be warming up to 150～200 ℃ gradually, evaporation makes solution become thick or colloidal to remove redundant moisture.
4. thick or colloidal compounding substances are placed muffle furnace, make it 600 ℃ of rapid spontaneous combustions down; Again 600～800 ℃ of roasting crystallizations 4～8 hours, get final product Li[Co XMn YNi (1-X-Y)] O 2Anode material for lithium-ion batteries.
Described transition metal manganese salt is soluble manganese salt, as manganese nitrate, manganese acetate etc.
Described transition metal cobalt salt is the solubility cobalt salt, as cobalt nitrate, cobalt acetate etc.
Described transition metal nickel salt is a soluble nickel salt, as nickel nitrate, nickel acetate etc.
Described lithium salts is the solubility lithium salts, as lithium nitrate, lithium acetate etc.
Described organic acid is to react with complexing of metal ion and with nitrate anion, and the glycine of burning takes place under the uniform temperature.
Preparation method of the present invention with have following advantage compared to existing technology:
1, process using liquid phase of the present invention and solid phase combination, the organic acid of Cai Yonging is a glycine simultaneously, in mixed solution glycine not only can with complexing of metal ion, form homogeneous phase, make to be reflected at ionic condition and to carry out, simultaneously can with nitrate anion generation redox reaction, burning rapidly under the uniform temperature, reaction is thoroughly complete, product yield height, product purity height, porous nickel, stable electrochemical property.
2, the raw material that adopts in the technology of the present invention, the impurity except that metal ion and oxonium ion does not leave impurity, so the product purity height overflowing reaction system with gaseous state in the spontaneous combustion rapidly in product.
3, the rapid spontaneous combustion in the technology of the present invention is similar to blast, and reaction is violent, makes that the product particle that generates is trickle, evenly, and has promoted reaction process effectively and has shortened the reaction time, and energy consumption is little, effectively reduces production cost.
4, the present invention is simple to operate, technology is easy to control, non-environmental-pollution, be easy to realize large-scale industrial production.
Embodiment
The present invention also can be described in further detail in conjunction with the embodiments:
Embodiment one:
A kind of preparation anode material for lithium-ion batteries LiCoO 2Method: 0.51mol (35.2g) lithium nitrate and 0.51mol (148.4g) cobalt nitrate hexahydrate are mixed and its aqueous solution of nitric acid with 1M are dissolved fully; Under constantly stirring, add the 61.3g glycine, be warming up to 200 ℃, become thick up to solution; Mixture of viscous form is placed muffle furnace, rapid spontaneous combustion takes place down at 600 ℃; 600 ℃ of roasting crystallizations 4 hours, can obtain LiCoO 2Anode material for lithium-ion batteries.Gained anode material for lithium-ion batteries LiCoO 2Be black powder, X-ray diffraction is accredited as pure phase, Li content 7.0% in the product, and Co content 60.4%, specific capacity is 140mAh/g, charges and discharge efficient during its charge and discharge cycles 20 times and still reaches 100.0%.
Embodiment two:
A kind of preparation anode material for lithium-ion batteries LiCo 0.8Ni 0.2O 2Method: 0.61mol (62.6g) acetate dihydrate lithium, 0.49mol (121.6g) Cobalt diacetate tetrahydrate and 0.12mol (35.5g) six water nickel nitrates are mixed, and its aqueous solution of nitric acid with 1M dissolved fully, under constantly stirring, add the 110.0g glycine, be warming up to 150 ℃ under constantly stirring, become thick up to solution; Mixture of viscous form is placed muffle furnace, and rapid spontaneous combustion takes place down at 600 ℃ in it; 700 ℃ of roasting crystallizations 6 hours, can obtain LiCo 0.8Ni 0.2O 2Anode material for lithium-ion batteries.Gained anode material for lithium-ion batteries LiCo 0.8Ni 0.2O 2Be black powder, X-ray diffraction is accredited as pure phase, Li content 7.2% in the product, and Co content 47.9%, Ni content 11.9%, specific capacity is 160mAh/g, charges and discharge efficient during its charge and discharge cycles 20 times and still reaches 99.8%.
Embodiment three:
A kind of preparation anode material for lithium-ion batteries LiCo 1/3Ni 1/3Mn 1/3O 2Method: 1.04mol (71.7g) lithium nitrate, 0.35mol (87.2g) Cobalt diacetate tetrahydrate, 0.35mol (87.1g) four water acetic acid nickel and 0.35mol (100.5g) six water manganese nitrates are mixed, and its aqueous solution of nitric acid with 1M dissolved fully, under constantly stirring, add the 313.6g glycine, be warming up to 150 ℃ under constantly stirring, become thick up to solution; Mixture of viscous form is placed muffle furnace, and rapid spontaneous combustion takes place down at 600 ℃ in it; 800 ℃ of roasting crystallizations 8 hours, can obtain LiCo 1/3Ni 1/3Mn 1/3O 2Anode material for lithium-ion batteries.Gained anode material for lithium-ion batteries LiCo 1/3Ni 1/3Mn 1/3O 2Be black-and-blue powder, X-ray diffraction is accredited as pure phase, Li content 7.1% in the product, and Co content 20.2%, Ni content 20.2%, Mn content 19.1%, specific capacity is 190mAh/g, charges and discharge efficient during its charge and discharge cycles 20 times and still reaches 99.8%.
Embodiment four:
A kind of preparation anode material for lithium-ion batteries LiCo 0.2Mn 0.8O 2Method: the cobalt nitrate hexahydrate of 0.85mol (86.7g) acetate dihydrate lithium, 0.17mol (49.5g) and 0.68mol (166.7g) four water acetic acid manganese are mixed, and its aqueous solution of nitric acid with 1M dissolved fully, under constantly stirring, add the 153.2g glycine, be warming up to 200 ℃ under constantly stirring, become thick up to solution; Mixture of viscous form is placed muffle furnace, and rapid spontaneous combustion takes place down at 600 ℃ in it; 800 ℃ of roasting crystallizations 6 hours, can obtain LiCo 0.2Mn 0.8O 2Anode material for lithium-ion batteries.Gained anode material for lithium-ion batteries LiCo 0.2Mn 0.8O 2Be black powder, X-ray diffraction is accredited as pure phase, Li content 7.2% in the product, Co content 12.3%, Mn content 46.3%.
Embodiment five:
A kind of preparation anode material for lithium-ion batteries LiMnO 2Method: 0.41mol (28.3g) lithium nitrate and 0.41mol (117.7g) six water manganese nitrates are mixed and its aqueous solution of nitric acid with 1M are dissolved fully; Under constantly stirring, add the 55.4g glycine, be warming up to 200 ℃, become thick up to solution; Mixture of viscous form is placed muffle furnace, rapid spontaneous combustion takes place down at 600 ℃; 600 ℃ of roasting crystallizations 5 hours, can obtain LiMnO 2Anode material for lithium-ion batteries.Gained anode material for lithium-ion batteries LiMnO 2Be black-and-blue powder, X-ray diffraction is accredited as pure phase, Li content 7.3% in the product, Mn content 58.6%.
Embodiment six:
A kind of preparation anode material for lithium-ion batteries LiNiO 2Method: 0.72mol (49.6g) lithium nitrate and 0.72mol (179.2g) four water acetic acid nickel are mixed and its aqueous solution of nitric acid with 1M are dissolved fully; Under constantly stirring, add the 108.1g glycine, be warming up to 200 ℃, become thick up to solution; Mixture of viscous form is placed muffle furnace, rapid spontaneous combustion takes place down at 600 ℃; 600 ℃ of roasting crystallizations 5 hours, can obtain LiNiO 2Anode material for lithium-ion batteries.Gained anode material for lithium-ion batteries LiNiO 2Be black powder, X-ray diffraction is accredited as pure phase, Li content 7.0% in the product, Ni content 60.3%.
Embodiment seven:
A kind of preparation anode material for lithium-ion batteries LiNi 1/2Mn 1/2O 2Method: 0.91mol (92.8g) acetate dihydrate lithium, 0.46mol (114.5g) four water acetic acid nickel and 0.46mol (132.0g) six water manganese nitrates are mixed and its aqueous solution of nitric acid with 1M are dissolved fully; Under constantly stirring, add the 261.0g glycine, be warming up to 200 ℃, become thick up to solution; Mixture of viscous form is placed muffle furnace, rapid spontaneous combustion takes place down at 600 ℃; 600 ℃ of roasting crystallizations 7 hours, can obtain LiNi 1/2Mn 1/2O 2Anode material for lithium-ion batteries.Gained anode material for lithium-ion batteries LiNi 1/2Mn 1/2O 2Be black powder, X-ray diffraction is accredited as pure phase, Li content 7.1% in the product, Ni content 30.7%, Mn content 28.5%.

Claims (7)

1, a kind of anode material for lithium-ion batteries is characterized in that: its chemical formula is composed as follows:
Li[Co X?Mn Y?Ni (1-X-Y)]O 2；
Wherein, 0≤X≤1,0≤Y≤1,0≤(X+Y)≤1.
2, a kind of preparation method of anode material for lithium-ion batteries according to claim 1 comprises following processing step:
1. lithium, transition metals cobalt, manganese, nickel salt are pressed 1: X: Y: (1-X-Y) amount of substance mixes, and dissolves fully with the aqueous solution of nitric acid of 1M, until obtaining homogeneous transparent solution; 0≤X≤1,0≤Y≤1,0≤(X+Y)≤1 wherein;
2. add organic acid in solution, this organic acid addition is 0.8: 1～2.0: 1 with the ratio of metal ion total amount;
3. under constantly stirring, the evaporation that heats up is warming up to 150～200 ℃ more gradually, and makes solution become thick or colloidal to remove redundant moisture;
4. thick or colloidal compounding substances are placed muffle furnace, make it 600 ℃ of rapid spontaneous combustions down; Again 600～800 ℃ of roasting crystallizations 4～8 hours, get final product Li[Co XMn YNi (1-X-Y)] O 2Anode material for lithium-ion batteries.
3, as the preparation method of anode material for lithium-ion batteries as described in the claim 2, it is characterized in that: described transition metal manganese salt is soluble manganese salt.
4, as the preparation method of anode material for lithium-ion batteries as described in the claim 2, it is characterized in that: described transition metal cobalt salt is the solubility cobalt salt.
5, as the preparation method of anode material for lithium-ion batteries as described in the claim 2, it is characterized in that: described transition metal nickel salt is a soluble nickel salt.
6, as the preparation method of anode material for lithium-ion batteries as described in the claim 2, it is characterized in that: described lithium salts is the solubility lithium salts.
7, as the preparation method of anode material for lithium-ion batteries as described in the claim 2, it is characterized in that: described organic acid is a glycine.
CNB2006101053088A 2006-12-14 2006-12-14 Method for preparing plus plate material of lithium ion battery by combustion method Expired - Fee Related CN100483807C (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103730635A (en) * 2013-12-18 2014-04-16 江苏科捷锂电池有限公司 Combustion method for preparing Li1.1Ni0.5Co0.2Mn0.3O2 lithium ion battery anode material
CN104091941A (en) * 2014-07-15 2014-10-08 长沙矿冶研究院有限责任公司 Lithium-rich and manganese-based anode material of layered lithium battery and preparation method thereof
CN106299328A (en) * 2015-05-14 2017-01-04 中国科学院物理研究所 Doping method, material and preparation method to lithium-rich oxide anode material
CN114212835A (en) * 2021-11-30 2022-03-22 天津巴莫科技有限责任公司 Simple preparation method of Al and Zr co-doped ultrahigh nickel ternary single crystal material

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1285134C (en) * 2003-10-28 2006-11-15 大同股份有限公司 Method for manufacturing lithiumi on secondary cell anode material

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103730635A (en) * 2013-12-18 2014-04-16 江苏科捷锂电池有限公司 Combustion method for preparing Li1.1Ni0.5Co0.2Mn0.3O2 lithium ion battery anode material
CN104091941A (en) * 2014-07-15 2014-10-08 长沙矿冶研究院有限责任公司 Lithium-rich and manganese-based anode material of layered lithium battery and preparation method thereof
CN106299328A (en) * 2015-05-14 2017-01-04 中国科学院物理研究所 Doping method, material and preparation method to lithium-rich oxide anode material
CN106299328B (en) * 2015-05-14 2019-11-08 中国科学院物理研究所 To the doping method of lithium-rich oxide anode material, material and preparation method
CN114212835A (en) * 2021-11-30 2022-03-22 天津巴莫科技有限责任公司 Simple preparation method of Al and Zr co-doped ultrahigh nickel ternary single crystal material

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