CN1160256C - Process for preparing nm-class lithium cobaltate by nm reactor - Google Patents
Process for preparing nm-class lithium cobaltate by nm reactor Download PDFInfo
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- CN1160256C CN1160256C CNB011295376A CN01129537A CN1160256C CN 1160256 C CN1160256 C CN 1160256C CN B011295376 A CNB011295376 A CN B011295376A CN 01129537 A CN01129537 A CN 01129537A CN 1160256 C CN1160256 C CN 1160256C
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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
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The present invention belongs to the technical field of chemical engineering. Cobalt nitrate and lithium hydroxide are used as raw materials and are respectively prepared into saturated solutions; sol is prepared through reactions in a nanometer reactor at normal temperature; after the sol is evaporated and dried, lithium cobaltate gelatin is prepared; after the lithium cobaltate gelatin is processed in a heat mode, lithium cobaltate nanometer powder used for a lithium cell is prepared. Lithium cobaltate products prepared by making use of the technique of the present invention have the advantages of good quality, stable performance and uniform particle diameters of particles; in general, the particle diameters of the particles are from 80 to 100 nm. Furthermore, the particle diameters of the lithium cobaltate powder products can be regulated by regulating the speed of a rotor of the nanometer reactor; lithium cobaltate powder products with different particle diameters can be prepared according to different requirements.
Description
Invention field
The invention belongs to chemical technology field, be specifically related to the preparation technology of the industrial cobalt acid of lithium cell powder for lithium.
Background technology
Nineteen ninety is at first succeeded in developing C/LiCoO by Japanese SONY Energy Development Corporation
2Lithium ion battery, and in realization commercialization in 1991.Canadian Moli energy company at first succeeded in developing C/LiNiO in 1991
2Lithium ion battery.Since then, research and use to lithium ion battery launch rapidly in worldwide, because lithium ion battery has the voltage height, the specific energy height, memory-less effect, characteristics such as non-environmental-pollution, especially comparing it with other battery has extended cycle life, safety performance is good, therefore since coming out, be widely used in mobile telephone, notebook computer, in the portable electric appts such as miniature camera, this battery also will be at electromobile as the power supply renewal product, the zone electronic information, ground such as satellite and spacecraft and space military field are widely used.Its market capacity enlarges day by day.
Along with the arrival of 21st century, the population growth, Economic development causes the mass consumption of the energy and the pollution of environment, and battery can replenish the energy and solve problem of environmental pollution.Battery is 21st century one of the world's ten big high-tech.The battery of 21st century has large vol, superpower, long lifetime, pollution-free, safe and reliable portable characteristics, be high-tech, high production, high profit, high foreign-exchange-earning export products, one of be called one of big high-tech of 21st century ten by external expert, or ten big money-making industries.Industry policy and subjective wishes from country, the national industry of country's encourage growth oneself, encourage oneself to produce starting material, oneself produces the lithium ion battery that has intellecture property, and homemade lithium ion battery occupies the due market share on huge Chinese market.In " 95 " national key scientific and technological project is listed hydrogen-nickel battery, lithium-ions battery, electromobile battery by State Planning Commission.There are three to be battery technology in 144 gordian techniquies in " 95 state key technological development guide " that State Economic and Trade Commission announces in December, 1997, " lithium ion battery ", " novel green battery and utilisation technology ", " mercury-free alkaline manganese dioxide battery technology and equipment and civilian secondary cell "; In 29 " high-capacity battery upgrading " arranged in " two high " transformation plan that this year, the tissue establishment was implemented once excellent.Former State Scientific and Technological Commission " 863 " classifies hydrogen-nickel battery, lithium-ions battery as the project of the most important thing in the works.Technical division of country classifies the novel high-energy store battery as high-tech industry, and in 833 of the National Torch Plan projects in 1999 of announcement, battery has 23, accounts for 27%; Battery also therein in 51 projects of nearest " 95 " most important thing of announcing.
Developed country partly turns to developing country such as China to the battery production seriously polluted, that labour intensity is high at present, such as the Cd-Ni battery is partly turned to the continent, and utilize vying each other between our inner enterprise, and buy the battery that we produce with extremely low price, resemble the Ni-MH battery.Conversely, the battery kind of their with high content of technology, cleanliness without any pollution is again because of our unable production gains high profits in Chinese market, such as lithium ion battery.They have difficulty in taking a step the research of our advanced battery technology and production by the control to patented technology and intellecture property etc. simultaneously.At present China produces lithium ion battery and mainly contains dual mode: (1) buys Japanese electric core, and oneself adds shell, and sell the packing back, earning be simple process cost.(2) buy Japanese starting material or external lithium cell starting material, oneself dress up electric core, mix shell again and sell.Since external prices of raw and semifnished materials height, and Japan presses the battery price very low, so the still process cost of Chinese Enterprise earning.Anode material for lithium ion battery mainly is cobalt acid lithium, lithium nickel cobalt dioxide and three kinds of materials of lithium manganate at present, and wherein cobalt acid lithium material accounts for the market more than 90%.Therefore, the electrode materials of exploitation lithium ion battery has good market outlook at home.
Summary of the invention
Purpose of the present invention is exactly to break abroad a kind of technology for preparing the industrial cobalt acid of lithium cell powder for lithium that the monopolization of cobalt acid lithium production technology is developed.
Main contents of the present invention:
Utilize Xiao Suangu and lithium hydroxide to be raw material, be mixed with saturated solution respectively, under the normal temperature in nano-reactor prepared in reaction colloidal sol, make cobalt acid lithium gel through pervaporation, drying process again, cobalt acid lithium gel is through Overheating Treatment, makes lithium cell with cobalt acid powder for lithium.
Concrete production stage is as follows:
(1) at first under 25 ℃, prepare the saturated solution of Xiao Suangu, lithium hydroxide respectively, solution prepares the back, and to add mass concentration in lithium hydroxide solution be 25% ammonia soln, the pH value of regulating lithium hydroxide solution is 10～12; Add citric acid in cobalt nitrate solution, the pH value of regulating cobalt nitrate solution is 3～6.
(2) Xiao Suangu and lithium hydroxide solution are proportionally fed in the nano-reactor react, the rotor speed of nano-reactor is 400～2000rpm.
(3) then the colloidal sol heating evaporation of gained is formed gel, and 120～140 ℃ of following vacuum-dryings 15～24 hours xerogel.
(4) at last with xerogel 400～550 ℃ of following thermal treatments 2～5 hours, obtain the industrial cobalt of lithium cell acid powder for lithium.
The spout speed that wherein the Xiao Suangu saturated solution is sprayed into nano-reactor is 3～20m/s, and the spout speed of lithium hydroxide saturated solution is 2～15m/s.
Fig. 1 is the test technology schema, cobalt nitrate solution and lithium hydroxide solution are supplied to the nano-reactor 1 from two storage tanks 2 by impeller pump 3 respectively, the flow of impeller pump 4 can be controlled according to spinner-type flowmeter, fully enters in the product receiving tank 5 after the reaction in nano-reactor 1.
Fig. 2 is the structural representation of nano-reactor, and it comprises housing 1, liquid inlet tube 2, axle envelope 3, axle 4, shaft coupling 5, filler 6, rotor 7, liquid outlet tube 8.Principle of work is as follows: reaction raw materials is entered in the filler by liquid inlet tube 2, drives rotor 7 rotations by axle 4, makes raw material fully react in filler 6.Nano-reactor can pass through frequency modulation speed change instrument (not showing in the drawings) and regulate rotating speed, and can reach the purpose of regulating the product particle diameter by regulating rotating speed.
This technology has solved high temperature solid-state method and low-temperature solid-phase method will be through the shortcoming of long-time high-temperature process; And And solved the shortcoming that solid phase method bulk cobalt acid lithium in Crushing with Jet Mill is stained with the fritter fragment; It is separated Complex process, the cost height that the traditional handicraft of having determined exists, grain diameter is inhomogeneous and wayward, product The shortcomings such as purity is inadequate. Processing step of the present invention is simple, equipment needed thereby and simple and take up an area little, investment Little, cost is low, pollution is little, productive rate is high, tally with the national condition. And the cobalt acid lithium that utilizes this technology to make Product, superior in quality, stable performance, grain diameter are even, and grain diameter is generally at 80～100nm, Meet the requirement of Lithium Battery Industry. And the grain diameter of cobalt acid lithium product can be by regulating the nanometer reaction The rotor speed of device is regulated, and can make according to different requirements the cobalt acid lithium product of variable grain particle diameter (such as the cobalt acid lithium of 5 μ m～10 μ m). The present invention will be the development of China's Lithium Battery Industry, provide excellent The cobalt acid lithium raw material of matter.
When temperature is normal temperature, 5000ml Xiao Suangu saturated solution is put into left storage tank, add the 100ml citric acid again; 3000ml lithium hydroxide saturated solution is put into right storage tank, add the 100ml mass concentration again and be 25% ammoniacal liquor.The cobalt nitrate solution flow is 120L/hr, and the lithium hydroxide solution flow is 80L/hr, sprays in the nano-reactor, and rotor speed is 500rpm.After reaction finished, the colloidal sol heating evaporation with gained formed gel then, and got xerogel in 24 hours 120 ℃ of following vacuum-dryings, at last with 400 ℃ of following thermal treatments of xerogel 2 hours, obtained the industrial cobalt acid of lithium cell lithium product.Product cut size 100～120nm, narrow particle size distribution.
When temperature is normal temperature, 5000ml Xiao Suangu saturated solution is put into left storage tank, add the 100ml citric acid again; 3000ml lithium hydroxide saturated solution is put into right storage tank, add the 100ml mass concentration again and be 25% ammoniacal liquor.The cobalt nitrate solution flow is 300L/hr, and the lithium hydroxide solution flow is 200L/hr, sprays in the nano-reactor, and rotor speed is 2000rpm.After reaction finished, the colloidal sol heating evaporation with gained formed gel then, and got xerogel in 24 hours 120 ℃ of following vacuum-dryings, at last with 400 ℃ of following thermal treatments of xerogel 2 hours, obtained the industrial cobalt acid of lithium cell lithium product.Product cut size 80～100nm, narrow particle size distribution.
When temperature is normal temperature, 5000ml Xiao Suangu saturated solution is put into left storage tank, add the 100ml citric acid again; 3000ml lithium hydroxide saturated solution is put into right storage tank, add the 100ml mass concentration again and be 25% ammoniacal liquor.The cobalt nitrate solution flow is 120L/hr, and the lithium hydroxide solution flow is 80L/hr, sprays in the nano-reactor, and rotor speed is 400rpm.After reaction finished, the colloidal sol heating evaporation with gained formed gel then, and got xerogel in 24 hours 120 ℃ of following vacuum-dryings, at last with 500 ℃ of following thermal treatments of xerogel 2 hours, obtained the industrial cobalt acid of lithium cell lithium product.Product cut size 5～6 μ m, narrow particle size distribution.
Claims (3)
1, the preparation technology of the industrial cobalt acid of lithium cell powder for lithium is characterized in that this technology may further comprise the steps successively:
(1) at first at normal temperatures, prepare the saturated solution of Xiao Suangu, lithium hydroxide respectively, it is 10～12 that solution prepares the pH value of regulating lithium hydroxide solution with citric acid in the back, and the pH value of regulating cobalt nitrate solution with ammoniacal liquor is 4～6;
(2) Xiao Suangu and lithium hydroxide solution are fed in the nano-reactor by 1.5: 1～2.0: 1 volume flow ratio react, the rotor speed of regulating nano-reactor is 400～2000rpm;
(3) then the colloidal sol heating evaporation of gained is formed gel, and carry out vacuum-drying, obtain xerogel;
(4) at last with 400～550 ℃ of following thermal treatments of xerogel 2～5 hours, obtaining the product granularity is the industrial cobalt acid of the lithium cell powder for lithium of 80nm-10 μ m.
2, the preparation technology of the industrial cobalt of lithium cell according to claim 1 acid powder for lithium, the spout speed that it is characterized in that the Xiao Suangu saturated solution is sprayed into nano-reactor is 3～20m/s, the spout speed of lithium hydroxide saturated solution is 2～15m/s.
3, the preparation technology of the industrial cobalt acid of lithium cell according to claim 1 powder for lithium is characterized in that the conversion unit employing temperature of reaction of cobalt acid lithium is a normal temperature, regulates the nano-reactor of rotating speed with frequency modulation speed change instrument.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB011295376A CN1160256C (en) | 2001-06-25 | 2001-06-25 | Process for preparing nm-class lithium cobaltate by nm reactor |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011295376A CN1160256C (en) | 2001-06-25 | 2001-06-25 | Process for preparing nm-class lithium cobaltate by nm reactor |
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| Publication Number | Publication Date |
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| CN1327951A CN1327951A (en) | 2001-12-26 |
| CN1160256C true CN1160256C (en) | 2004-08-04 |
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| CNB011295376A Expired - Fee Related CN1160256C (en) | 2001-06-25 | 2001-06-25 | Process for preparing nm-class lithium cobaltate by nm reactor |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2003080517A1 (en) * | 2002-03-26 | 2003-10-02 | Council Of Scientific And Industrial Research | Solid state thermal synthesis of lithium cobaltate |
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