CN102344168B - Method for synthesizing high tap density spinel material LiNi0.5Mn1.5O4 - Google Patents
Method for synthesizing high tap density spinel material LiNi0.5Mn1.5O4 Download PDFInfo
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- CN102344168B CN102344168B CN 201110186663 CN201110186663A CN102344168B CN 102344168 B CN102344168 B CN 102344168B CN 201110186663 CN201110186663 CN 201110186663 CN 201110186663 A CN201110186663 A CN 201110186663A CN 102344168 B CN102344168 B CN 102344168B
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Abstract
The invention discloses a method for synthesizing a high tap density spinel material LiNi0.5Mn1.5O4. The method is characterized by comprising the steps of: (1) dissolving a lithium salt, a nickel salt, a manganese salt and an additive in certain proportion in deionized water, stirring and heating the water so as to form a sol mixture; (2) presintering the sol at a specific temperature for a specific period of time, thus obtaining a primary product; (3) subjecting the primary product to high temperature formal sintering for a specific period of time under a specific temperature, thus obtaining an end product. The process of the invention has the characteristics of simple gel forming method, short production period, lower energy consumption, less hidden dangers in large scale production, and low production cost, etc. And the spinel-type nickel lithium manganate positive material prepared by the method of the invention has the advantages of high product purity, high tap density, uniformproduct particle and stable electrochemical performance.
Description
Technical field
The invention belongs to the synthetic field of inorganic functional material, be fit to the preparation of high tap density lithium ion battery 5V level positive electrode material.
Background technology
Generally the anode material for lithium-ion batteries of charge and discharge platform more than 4.5V is called the noble potential positive electrode material, or 5V level positive electrode material, according to present result of study, this class noble potential positive electrode material mainly contains spinel type LiM
xMn
2-xO
4(0≤x≤1, M is iron, copper, cobalt, nickel, chromium and transition metal of the same clan thereof) here, olivine-type LiMPO
4(M is cobalt, nickel, chromium and transition metal of the same clan thereof), and the material of some other laminate structures.Wherein, (chemical formula is: LiNi to have the spinel nickel lithium manganate material of 4.7V voltage platform
0.5Mn
1.5O
4), no matter be all to be proved from Theoretical Calculation or from the preparation research in laboratory to have excellent application prospect, be a focus of present high-potential material exploitation.
Have the high-potential material nickel lithium manganate of 5V level charge and discharge platform because of higher more than 30% than traditional cobalt acid lithium voltage (3.7V), be suitable for the needs of high power battery.Through years of development, along with the development of high-potential material supporting technology (for example noble potential electrolytic solution), high-potential material nickel lithium manganate moves towards the practicability exploitation from technology of preparing, basic Electrochemical Properties etc. gradually.For example, " nickel lithium manganate-lithium titanate " battery of the Ohzuku of Osaka, Japan City University and the cooperation of SANYO electronics assembling capability retention of 90% in addition that under 2C, circulate after 2000 times; Korea S's LG chemistry has been manufactured experimently 600mAh's " nickel lithium manganate-graphite " soft-package battery; French CE A subordinate's liten company has manufactured experimently 2Ah's " nickel lithium manganate-graphite " soft-package battery; The ETVM company of Israel then with such " nickel lithium manganate-graphite " battery successful Application on telecontrolled aircraft.Other side, the Daikin Industries of Japan has also been released the fluorine-containing electrolyte that can be used for the 4.7V voltage platform at the application requiring of noble potential nickel lithium manganate; U.S. Enerdel company is then just carrying out under the subsidy of USDOE and can be used for plug-in hybrid automobile-used " nickel lithium manganate-lithium titanate " battery research
At present, the industrialization development of noble potential anode material nickel lithium manganate has welcome important opportunity, particularly under the situation of national new forms of energy industry fast development, at have the variety of problems that various anodal equivalent material occur now in practicality, and in the large-sized power field of batteries, energy-storage battery fields etc. are to the security of battery material of new generation, work-ing life, the harsh requirement that aspects such as cost propose, noble potential nickel lithium manganate material is to be hopeful most to obtain the revolutionary lithium ion anode material of breaking through in lithium electricity industry, becomes the key player of new energy field.
Employing ethanol such as Yu Zuolong are that dispersion medium prepares nickel lithium manganate material (CN 101844817 A), and this patent described " sol-gel-self-propagating combustion " because will contain the combustion processes of a large amount of ethanol colloidal sols and may cause the combustion explosion potential safety hazard to limit its application in industrialized production through one.In addition, the route that the liquid phase method that comprises many pieces of bibliographical informations of above-mentioned patent prepares the nickel lithium manganate often is difficult for improving the tap density of product, and this has also limited the application of prepared electrode materials in the actual battery production technique.
Summary of the invention
The purpose of this invention is to provide a kind of low cost, easily mass-producing, the safe method for the preparation of high tap density 5V level anode material for lithium-ion batteries spinel type nickel lithium manganate of industrial operation,
Method for the preparation of high tap density 5V level anode material for lithium-ion batteries spinel type nickel lithium manganate: preparation of raw material is become colloidal sol, this colloidal sol is obtained final product through pre-burning, formal calcination processing.It is simple that this process has into a gluing method; with short production cycle; characteristics such as energy consumption is low, potential safety hazard is few in the large-scale production, production cost is few, and spinel type nickel manganate cathode material for lithium product purity height, tap density height, product uniform particles by this method preparation, stable electrochemical property.
Below be the narration about the present invention's " a kind of method for preparing high tap density 5V level anode material for lithium-ion batteries spinel type nickel lithium manganate ":
Preparation method of the present invention comprises following processing step:
This colloidal sol is being obtained head product under the specified temp after the specified time pre-burning;
According to technological line provided by the invention, it is characterized in that: the employing deionized water is solvent, reaching relevant auxiliary agent with lithium, nickel, manganic compound is raw material, form colloidal sol, be implemented in the even dispersion on the molecular level, through drying, dehydration, low temperature presintering, the high-temperature calcination of necessity, finally form the good nickel lithium manganate product of chemical property.
According to technological line of the present invention, the lithium salts that adopts comprises Quilonum Retard, lithium hydroxide, lithium nitrate, reaches the mixture of one or more several salt in the various carboxylic acid lithium salts such as lithium formate, lithium acetate; The nickel salt that adopts comprises the mixture of one or both salt in nickelous nitrate, the nickelous acetate, and the nickelous nitrate, the nickelous acetate that are obtained through nitrification, acetic acid reaction by nickel raw materials such as metallic nickel, nickel hydroxide, nickelous carbonate, nickel oxide; The manganese salt that adopts comprises the mixture of one or both salt in manganous nitrate, the manganous acetate,, and the manganous nitrate, the manganous acetate that are obtained through nitrification, acetic acid reaction by nickel raw materials such as manganese metal, manganous hydroxide, manganous carbonate, manganese oxide; Wherein, the mol ratio of lithium salts, nickel salt and its lithium of manganese salt, nickel, manganese is: n
Li: n
Ni: n
Mn=1.95 ~ 2.2:1.0 ~ 1.1:3.0, top condition is n
Li: n
Ni: n
Mn=2.1: 1.05: 3.0.The auxiliary agent that adopts comprises the mixture of one or more the two kinds of salt in citric acid, the urea, and adjuvant used quality and the mass ratio of final product are m
Auxiliary agent: m
Product=1 ~ 3:2, top condition is m
Auxiliary agent: m
Product=1:1.
According to technological line of the present invention, the acquisition mode of elementary product is a kind of in following several mode: 1. colloidal sol directly heats pre-burning under specified temp; 2. colloidal sol obtains dried powder by spraying drying, pre-burning under given conditions more earlier; 3. colloidal sol directly carries out spray pyrolysis under given conditions; The temperature limit of described colloidal sol pre-burning fixes between 300 ℃ ~ 600 ℃, and the pre-burning time is 0 ~ 6 hour.Top condition be 550 ℃ following 3 hours.
According to technological line of the present invention, the head product that obtains after the colloidal sol pre-burning must could finally obtain spinel type nickel lithium manganate through the high-temperature calcination under the specified conditions, the temperature limit that adopts fixes between 600 ℃ ~ 850 ℃, the pre-burning time is 3 ~ 24 hours, top condition be 800 ℃ following 12 hours.
The preparation method of lithium ion secondary battery anode material of the present invention compared with prior art has following advantage:
1. the present invention has realized the even mixing of reaction raw materials on molecular level by the mode that forms liquid phase colloidal sol;
2. the present invention has reduced the quantity of the needed citric acid of conventional gel method by coordination between the contained metal ion of raw material self and the carboxyl, has reduced production cost;
3. the present invention is simple to operate, technology is easy to control, non-environmental-pollution;
4. the present invention adopts water to make solvent, is difficult for causing security incident in large-scale production;
5. the product that obtains of the present invention is compared characteristics such as having the tap density height with the product that the common sol method obtains, and uses processibility good in lithium ion battery, is conducive to improve the energy density of battery.
Description of drawings
Fig. 1 is the LiNi that utilizes the present invention to prepare
0.5Mn
1.5O
4The crystal morphology figure of positive electrode material;
Fig. 2 is the LiNi that utilizes the present invention to prepare
0.5Mn
1.5O
4Charging and discharging curve behind positive electrode material and the metallic lithium composition CR2032 type button cell under 0.2C;
Fig. 3 is the LiNi that utilizes the present invention to prepare
0.5Mn
1.5O
4Charging and discharging curve behind positive electrode material and the metallic lithium composition CR2032 type button cell under 10C;
Fig. 4 is the LiNi that utilizes the present invention to prepare
0.5Mn
1.5O
4Cycle performance behind positive electrode material and the metallic lithium composition CR2032 type button cell under 2C.
Embodiment
Being raw material with Quilonum Retard, nickelous nitrate, manganous acetate, citric acid, Glacial acetic acid, is dispersion agent with water, and wherein by Li: the ratio of Ni: Mn is to mix (mol ratio, down with) at 1: 0.5: 1.5.Earlier Quilonum Retard is added the reaction of capacity Glacial acetic acid and form Lithium Acetate, join then in the nickel nitrate solution, again manganous acetate, citric acid are joined in the above-mentioned solution colloidal sol that stirring and heating have obvious viscosity until formation; The spray-dried formation powder of this colloidal sol is calcined this powder 12 hours down for 3 hours, 750 ℃ through 350 ℃ of following pre-burnings, obtains final product, and tap density is 2.3g/cm
3This product is through being assembled into battery testing, and the test specific storage is more than the 145mAh/g under 0.2C condition between 3.5V ~ 5.2V, and the test specific storage is more than the 121mAh/g under the 10C condition, and the capability retention under the 2C after the circulation 800 times is more than 88%.
Embodiment 2
Being raw material with Quilonum Retard, nickelous nitrate, manganous acetate, citric acid, Glacial acetic acid, is dispersion agent with water, and wherein by Li: the ratio of Ni: Mn is to mix (mol ratio, down with) at 1.05: 0.5: 1.5.Earlier Quilonum Retard is added the reaction of capacity Glacial acetic acid and form Lithium Acetate, join then in the nickel nitrate solution, again manganous acetate, citric acid are joined in the above-mentioned solution colloidal sol that stirring and heating have obvious viscosity until formation; The spray-dried formation powder of this colloidal sol is calcined this powder 12 hours down for 1 hour, 800 ℃ through 450 ℃ of following pre-burnings, obtains final product, and tap density is 2.5g/cm
3This product is through being assembled into battery testing, and the test specific storage is more than the 143mAh/g under 0.2C condition between 3.5V ~ 5.2V, and the test specific storage is more than the 117mAh/g under the 10C condition, and the capability retention under the 2C after the circulation 100 times is more than 90%.
Embodiment 3
Being raw material with Quilonum Retard, nickelous nitrate, manganous acetate, citric acid, Glacial acetic acid, is dispersion agent with water, and wherein by Li: the ratio of Ni: Mn is to mix (mol ratio, down with) at 1.: 0.52: 1.5.Earlier Quilonum Retard is added the reaction of capacity Glacial acetic acid and form Lithium Acetate, join then in the nickel nitrate solution, again manganous acetate, citric acid are joined in the above-mentioned solution colloidal sol that stirring and heating have obvious viscosity until formation; The spray-dried formation powder of this colloidal sol is calcined this powder 3 hours down for 1 hour, 800 ℃ through 550 ℃ of following pre-burnings, obtains final product, and tap density is 2.38g/cm
3This product is through being assembled into battery testing, and the test specific storage is more than the 146mAh/g under 0.2C condition between 3.5V ~ 5.2V, and the test specific storage is more than the 119mAh/g under the 10C condition, and the capability retention under the 2C after the circulation 500 times is more than 95%.
Embodiment 4
Being raw material with lithium hydroxide, nickelous nitrate, manganous acetate, citric acid, Glacial acetic acid, is dispersion agent with water, and wherein by Li: the ratio of Ni: Mn is to mix (mol ratio, down with) at 1: 0.5: 1.5.Earlier lithium hydroxide is added the reaction of capacity Glacial acetic acid and form Lithium Acetate, join then in the nickel nitrate solution, again manganous acetate, citric acid are joined in the above-mentioned solution colloidal sol that stirring and heating have obvious viscosity until formation; The spray-dried formation powder of this colloidal sol is calcined this powder 12 hours down for 1 hour, 750 ℃ through 550 ℃ of following pre-burnings, obtains final product, and tap density is 2.3g/cm
3This product is through being assembled into battery testing, and the test specific storage is more than the 144mAh/g under 0.2C condition between 3.5V ~ 5.2V, and the test specific storage is more than the 117mAh/g under the 10C condition, and the capability retention under the 2C after the circulation 200 times is more than 99%.
Embodiment 5
Being raw material with Lithium Acetate, metallic nickel, manganous acetate, citric acid, nitric acid, is dispersion agent with water, and wherein by Li: the ratio of Ni: Mn is to mix (mol ratio, down with) at 1: 0.5: 1.5.Earlier metallic nickel is added the capacity nitric acid reaction and form nickel nitrate solution, then Lithium Acetate is joined in the above-mentioned nickelous nitrate solution, again manganous acetate, citric acid are joined in the above-mentioned solution colloidal sol that stirring and heating have obvious viscosity until formation; The spray-dried formation powder of this colloidal sol is calcined this powder 6 hours down for 2 hours, 750 ℃ through 500 ℃ of following pre-burnings, obtains final product, and tap density is 2.45g/cm
3This product is through being assembled into battery testing, and the test specific storage is more than the 141mAh/g under 0.2C condition between 3.5V ~ 5.2V, and the test specific storage is more than the 115mAh/g under the 10C condition, and the capability retention under the 2C after the circulation 200 times is more than 97%.
Embodiment 6
Being raw material with Lithium Acetate, nickelous carbonate, manganous acetate, citric acid, nitric acid, is dispersion agent with water, and wherein by Li: the ratio of Ni: Mn is to mix (mol ratio, down with) at 1.1: 0.5: 1.5.Earlier nickelous carbonate is added the capacity nitric acid reaction and form nickel nitrate solution, then Lithium Acetate is joined in the above-mentioned nickelous nitrate solution, again manganous acetate, citric acid are joined in the above-mentioned solution colloidal sol that stirring and heating have obvious viscosity until formation; The spray-dried formation powder of this colloidal sol is calcined this powder 18 hours down for 5 hours, 750 ℃ through 500 ℃ of following pre-burnings, obtains final product, and tap density is 2.6g/cm
3This product is through being assembled into battery testing, and the test specific storage is more than the 139mAh/g under 0.2C condition between 3.5V ~ 5.2V, and the test specific storage is more than the 112mAh/g under the 10C condition, and the capability retention under the 2C after the circulation 200 times is 100%.
Embodiment 7
Being raw material with Lithium Acetate, nickelous nitrate, manganous carbonate, urea, Glacial acetic acid, is dispersion agent with water, and wherein by Li: the ratio of Ni: Mn is to mix (mol ratio, down with) at 1: 0.5: 1.5.Earlier manganous carbonate is added the reaction of capacity Glacial acetic acid and form manganese acetate solution, join in the above-mentioned solution colloidal sol that stirring and heating have obvious viscosity until formation then with Lithium Acetate, nickelous nitrate, citric acid; The spray-dried formation powder of this colloidal sol is calcined this powder 18 hours down for 5 hours, 750 ℃ through 500 ℃ of following pre-burnings, obtains final product, and tap density is 2.65g/cm
3This product is through being assembled into battery testing, and the test specific storage is more than the 139mAh/g under 0.2C condition between 3.5V ~ 5.2V, and the test specific storage is more than the 112mAh/g under the 10C condition, and the capability retention under the 2C after the circulation 200 times is 100%.
Claims (1)
1. synthetic high tap density spinel LiNi
0.5Mn
1.5O
4Method, it is characterized in that, may further comprise the steps and carry out:
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| CN102903897A (en) * | 2012-07-20 | 2013-01-30 | 合肥国轩高科动力能源有限公司 | Method for preparing nickel lithium manganate having spinel structure by static mixer type reactor |
| CN102800856A (en) * | 2012-08-31 | 2012-11-28 | 株洲天地龙电源科技有限公司 | Preparation method of manganic acid-nickel-lithium positive electrode with high specific energy and high power |
| CN111018005A (en) * | 2019-12-06 | 2020-04-17 | 贵州大龙汇成新材料有限公司 | Spinel type lithium nickel manganese oxide material and preparation method thereof |
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Denomination of invention: A method for the synthesis of high tap density spinel materials LiNi0.5Mn1.5O4 Effective date of registration: 20131127 Granted publication date: 20130911 Pledgee: Chengdu joint venture finance Company limited by guarantee Pledgor: Chengdu Xingneng New Materials Co.,Ltd. Registration number: 2013510000009 |
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