CN102107862A - Method for preparing lithium iron phosphate by using wood fibers as carbon source - Google Patents
Method for preparing lithium iron phosphate by using wood fibers as carbon source Download PDFInfo
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- CN102107862A CN102107862A CN2011100230067A CN201110023006A CN102107862A CN 102107862 A CN102107862 A CN 102107862A CN 2011100230067 A CN2011100230067 A CN 2011100230067A CN 201110023006 A CN201110023006 A CN 201110023006A CN 102107862 A CN102107862 A CN 102107862A
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Abstract
The invention discloses a method for preparing lithium iron phosphate by using wood fibers as a carbon source, which comprises the following steps: adding a lithium source, an iron source and a phosphorus source into a ball milling tank according to the element ratio of 1:1:1, adding lignocellulose which accounts for 5-35% by mass of the yield of the lithium iron phosphate, evenly mixing by wet ball milling, and ensuring that the carbon content in the final lithium iron phosphate product is 0-10% by mass; drying in the air, thoroughly grinding, and presintering under the protection of an inert atmosphere; and thoroughly grinding the presintered material, sintering the material in an inert protective atmosphere, and grinding the sintered product to obtain the lithium iron phosphate powder. The method disclosed by the invention is used for preparing a compound LiFePO4 by using wood fibers as a carbon source. The method is simple and feasible, and has the advantage of low cost; and the prepared product has the advantages of high electric conductivity and excellent electrochemical properties, and has broad market application prospects.
Description
Technical field
The present invention relates to the preparation method of lithium ion battery electrode material, a kind of method of utilizing wood fibre to prepare iron lithium phosphate as carbon source of more specifically saying so.
Background technology
Since Sony company in 1991 releases the commodity lithium ion battery first, through the development in 20 years, lithium ion battery with its open circuit voltage height, have extended cycle life, energy density height, self-discharge are low, memory-less effect, advantage such as environmentally friendly are widely used in people's work, study, life all respects.In recent years, along with the market requirement of power cell and large-scale power energy storage device constantly increases, occurred successively with the power and the accumulation power supply of lithium ion battery as carrier.Because traditional positive pole material of lithium cobalt acid is at cost, environment friendly, and the open defect in the security, has limited its market and used.The iron lithium phosphate molecular formula is LiFePO
4, it is as a kind of new type lithium ion battery positive electrode material, and more traditional lithium ion battery material has remarkable advantages in cost, the feature of environmental protection, life-span and security, thereby becomes the preferred material of following power cell and large-scale lithium-ion energy storage device.But LiFePO 4 material itself also exists the inherent defective, and its ion and electronic conductivity are all not ideal enough, thus under low temperature and high current charge-discharge condition poor-performing.Iron in the iron lithium phosphate is ferrous iron in addition, if adopt the divalence source of iron can increase the production difficulty as raw materials for production, improves production cost.
At the above shortcoming of iron lithium phosphate, the present invention mainly by adopting cheap wood fibre as carbon source, carries out surface carbon to product and is coated with its production cost of reduction and improves its performance; In addition by adopting the ferric iron raw material to reduce production costs as source of iron.
Summary of the invention
The present invention is by adopting wood fibre as carbon source, and by solid reaction process, carbothermic reduction prepares high-performance iron phosphate lithium, has guaranteed the high-performance of product when having reduced cost.
The technical solution used in the present invention is: utilize wood fibre to prepare the method for iron lithium phosphate as carbon source, it is characterized in that carrying out as follows: lithium source, source of iron, phosphorus source are added in the ball grinder than Li:Fe:P=1:1:1 according to the amount of elemental substance, the lignocellulose that adds iron lithium phosphate output 5% ~ 35% quality again, mix with wet ball grinding, and guarantee that the quality carbon content is 0-10% in the final iron lithium phosphate product; In air, behind 30～80 ℃ of down dry 1～48h, under inert atmosphere protection, carry out pre-burning with 200～500 ℃ of insulation 2～20h through fully grinding again; Material after the pre-burning is positioned over once more under the inert protective atmosphere after fully grinding and is incubated 2～20h sintering with 550～900 ℃, and the product behind the sintering obtains LiFePO 4 powder after grinding.
Among the above-mentioned preparation method, the lithium source is at least a in Quilonum Retard, monometallic, Lithium Acetate, lithium nitrate, the lithium hydroxide.
Among the above-mentioned preparation method, source of iron is at least a in Ferrox, Iron diacetate, ironic oxalate, iron acetate, iron nitrate, tertiary iron phosphate, the ferric oxide.
Among the above-mentioned preparation method, the phosphorus source is at least a in ammonium phosphate, primary ammonium phosphate, Secondary ammonium phosphate, the tertiary iron phosphate.
Among the above-mentioned preparation method, carbon source is at least a in lignocellulose, trees sawdust, maize straw, hemp stalk, straw, straw, bagasse, paper, the cotton.
Among the above-mentioned preparation method, raw material mixed grinding medium is at least a in deionized water, distilled water, industrial spirit, dehydrated alcohol, the acetone.
Among the above-mentioned preparation method, inert protective atmosphere is at least a in argon gas, nitrogen, helium, the hydrogen.
Compared with the prior art, beneficial effect of the present invention is embodied in: present method is chosen starting material and is common raw material, and cost is very low.In addition, the main batch mixing and the synthetic method of present method are solid reaction process, help promoting aborning.The iron lithium phosphate of preparing with this method has gratifying chemical property, and loading capacity is higher, and high rate performance, cycle performance are outstanding.Therefore, on lithium ion power and energy-storage battery, good prospects for application is arranged.
Description of drawings
Fig. 1 is the LiFePO of preparation in the embodiment of the invention 1
4X-ray diffraction (XRD) figure.
Fig. 2 is the partial L iFePO of preparation in the embodiment of the invention 1 ~ 4
4Scanning electron microscope (SEM) figure.
Fig. 3 is the partial L iFePO of preparation in the embodiment of the invention 2 ~ 4
4X-ray diffraction (XRD) figure.
Fig. 4 is in the embodiment of the invention 1, and raw material contains the 1.5g lignocellulose, and sintering temperature is 630 ℃, the LiFePO that sintering time prepares during for 10h
425 ℃ of following voltage-specific storage graphic representations.
The invention will be further described below in conjunction with embodiment.
Embodiment
Embodiment 1:
1,0.025mol Quilonum Retard, 0.025mol ferric oxide, 0.05mol primary ammonium phosphate, 0.5 ~ 2g lignocellulose are added in the ball grinder, add 40ml acetone, with wet ball grinding mixing 24h;
2, descend dry 2h to complete drying at 120 ℃ in the slurry behind the wet ball grinding;
3, under inert atmosphere protection, carry out pre-burning with 350 ℃ of insulation 10h.Material after the pre-burning is positioned over after fully grinding under the inert protective atmosphere once more with 600 ~ 650 ℃ of insulation 5 ~ 15h sintering;
4, the product behind the sintering obtains LiFePO 4 powder after grinding;
5, the result characterizes:
(1) as can be seen, the final product that obtains under the various conditions is the iron lithium phosphate of pure phase olivine-type structure, does not have obvious crystalline phase impurity and exists by accompanying drawing 1;
(2) as can be seen, the product primary particle is the class sphere, about 500 nm of median size by accompanying drawing 2;
(3) as can be seen by subordinate list 1 and accompanying drawing 4, the 03-2 product under 25 ℃, 0.2,1,2, during the 5C multiplying power, first discharge specific capacity is respectively 135,128,117,98mAh/g.
Embodiment 2:
1,0.025mol Quilonum Retard, 0.05mol Ferrox, 0.05mol primary ammonium phosphate, 0.5 ~ 2g lignocellulose are added in the ball grinder, add 40ml acetone, with wet ball grinding mixing 24h;
2, descend dry 2h to complete drying at 120 ℃ in the slurry behind the wet ball grinding;
3, under inert atmosphere protection, carry out pre-burning with 350 ℃ of insulation 10h.Material after the pre-burning is positioned over after fully grinding under the inert protective atmosphere once more with 600 ~ 650 ℃ of insulation 5 ~ 15h sintering;
4, the product behind the sintering obtains LiFePO 4 powder after grinding;
5, the result characterizes:
(1) as can be seen, the final product that obtains is the iron lithium phosphate of pure phase olivine-type structure, does not have obvious crystalline phase impurity and exists by accompanying drawing 3;
(2) as can be seen, the product primary particle is the class sphere, the about 300nm of median size by accompanying drawing 2;
(3) as can be seen by subordinate list 2, the 03-2 product under 25 ℃, 0.2,1,2, during the 5C multiplying power, first discharge specific capacity is respectively 134,126,119,95mAh/g.
Embodiment 3:
1,0.05mol monometallic, 0.025mol ferric oxide, 0.5 ~ 2g lignocellulose are added in the ball mill, add 40ml acetone, with wet ball grinding mixing 2h;
2, descend dry 2h to complete drying at 120 ℃ in the slurry behind the wet ball grinding;
3, under inert atmosphere protection, carry out pre-burning with 350 ℃ of insulation 10h.Material after the pre-burning is positioned over after fully grinding under the inert protective atmosphere once more with 600 ~ 650 ℃ of insulation 5 ~ 15h sintering;
4, the product behind the sintering obtains LiFePO 4 powder after grinding;
5, the result characterizes:
(1) as can be seen, the final product that obtains is the iron lithium phosphate of pure phase olivine-type structure, does not have obvious crystalline phase impurity and exists by accompanying drawing 3;
(2) as can be seen, the product primary particle is the class sphere, the about 500nm of median size by accompanying drawing 2;
(3) as can be seen by subordinate list 3, the 03-2 product under 25 ℃, 0.2,1,2, during the 5C multiplying power, first discharge specific capacity is respectively 134,123,115,96mAh/g.
Embodiment 4:
1,0.05mol Quilonum Retard, 0.05mol tertiary iron phosphate, 0.5 ~ 2g lignocellulose are added in the ball mill, add 40ml acetone, with wet ball grinding mixing 24h;
2, descend dry 2h to complete drying at 120 ℃ in the slurry behind the wet ball grinding;
3, under inert atmosphere protection, carry out pre-burning with 350 ℃ of insulation 10h.Material after the pre-burning is positioned over after fully grinding under the inert protective atmosphere once more with 600 ~ 650 ℃ of insulation 5 ~ 15h sintering;
4, the product behind the sintering obtains LiFePO 4 powder after grinding;
5, the result characterizes:
(1) as can be seen, the final product that obtains is the iron lithium phosphate of pure phase olivine-type structure, does not have obvious crystalline phase impurity and exists by accompanying drawing 3;
(2) as can be seen, the product primary particle is the class sphere, the about 300nm of median size by accompanying drawing 2;
(3) as can be seen by accompanying drawing 5 tables 4, product under 25 ℃, 0.2,1,2, during the 5C multiplying power, first discharge specific capacity is respectively 134,126,114,95mAh/g;
Table 1 ~ 4 are respectively the LiFePO of preparation in the foregoing description 1 ~ 4
4At different carbon source ratios, the specific discharge capacity of different sintering temperatures and different sintering times.
More than four kinds of embodiments the result as can be seen, can prepare the iron lithium phosphate of pure phase as carbon source with the wood fibre of cheapness.The iron lithium phosphate good crystallinity of preparing, primary particle is little and even.Chemical property comprises that specific storage, cycle performance are all very excellent, makes us its application prospect is full of expectation.
In a word, it is a feasibility height that wood fibre prepares iron lithium phosphate as carbon source, and cost is lower, and the preparation technology of good application prospect is arranged.
Claims (7)
1. utilize wood fibre to prepare the method for iron lithium phosphate as carbon source, it is characterized in that carrying out as follows: lithium source, source of iron, phosphorus source are added in the ball grinder than Li:Fe:P=1:1:1 according to the amount of elemental substance, the lignocellulose that adds iron lithium phosphate output 5% ~ 35% quality again, mix with wet ball grinding, and guarantee that the quality carbon content is 0-10% in the final iron lithium phosphate product; In air, behind 30～80 ℃ of down dry 1～48h, under inert atmosphere protection, carry out pre-burning with 200～500 ℃ of insulation 2～20h through fully grinding again; Material after the pre-burning is positioned over once more under the inert protective atmosphere after fully grinding and is incubated 2～20h sintering with 550～900 ℃, and the product behind the sintering obtains LiFePO 4 powder after grinding.
2. preparation method according to claim 1 is characterized in that described lithium source is at least a in Quilonum Retard, monometallic, Lithium Acetate, lithium nitrate, the lithium hydroxide.
3. preparation method according to claim 1 is characterized in that described source of iron is at least a in Ferrox, Iron diacetate, ironic oxalate, iron acetate, iron nitrate, tertiary iron phosphate, the ferric oxide.
4. preparation method according to claim 1 is characterized in that described phosphorus source is at least a in ammonium phosphate, primary ammonium phosphate, Secondary ammonium phosphate, the tertiary iron phosphate.
5. preparation method according to claim 1 is characterized in that described carbon source is at least a in lignocellulose, trees sawdust, maize straw, hemp stalk, straw, straw, bagasse, paper, the cotton.
6. preparation method according to claim 1 is characterized in that described raw material mixed grinding medium is at least a in deionized water, distilled water, industrial spirit, dehydrated alcohol, the acetone.
7. preparation method according to claim 1 is characterized in that described inert protective atmosphere is at least a in argon gas, nitrogen, helium, the hydrogen.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102361071A (en) * | 2011-06-27 | 2012-02-22 | 湖南中天新能源有限公司 | Preparation method for modified LiFePO4 lithium ion battery anode material |
| CN102386411A (en) * | 2011-11-10 | 2012-03-21 | 山东精工电子科技有限公司 | High-capacity lithium ion battery anode material LiFePO4/C and preparation method thereof |
| CN103342369A (en) * | 2013-06-08 | 2013-10-09 | 合肥国轩高科动力能源股份公司 | Method for synthesizing silicate cathode material by taking rice husk as raw material |
| CN103682342A (en) * | 2013-12-26 | 2014-03-26 | 山东精工电子科技有限公司 | Lithium iron phosphate preparation method for improving tap density and specific capacity |
| CN103996843A (en) * | 2014-05-23 | 2014-08-20 | 桂林电子科技大学 | Porous lithium manganate nanosheet and preparation method thereof |
| CN106146905A (en) * | 2016-08-01 | 2016-11-23 | 云南大学 | A kind of preparation method of half-natural material artificial carbon source material |
| CN106698383A (en) * | 2017-01-20 | 2017-05-24 | 中天储能科技有限公司 | Method of preparing lithium iron phosphate material by using coconut fibers |
| CN115020659A (en) * | 2022-01-21 | 2022-09-06 | 昆明理工大学 | LiFePO 4 Preparation method of/C composite positive electrode material |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102361071A (en) * | 2011-06-27 | 2012-02-22 | 湖南中天新能源有限公司 | Preparation method for modified LiFePO4 lithium ion battery anode material |
| CN102386411A (en) * | 2011-11-10 | 2012-03-21 | 山东精工电子科技有限公司 | High-capacity lithium ion battery anode material LiFePO4/C and preparation method thereof |
| CN103342369A (en) * | 2013-06-08 | 2013-10-09 | 合肥国轩高科动力能源股份公司 | Method for synthesizing silicate cathode material by taking rice husk as raw material |
| CN103682342A (en) * | 2013-12-26 | 2014-03-26 | 山东精工电子科技有限公司 | Lithium iron phosphate preparation method for improving tap density and specific capacity |
| CN103682342B (en) * | 2013-12-26 | 2016-02-24 | 山东精工电子科技有限公司 | A kind of lithium iron phosphate preparation method improving tap density and specific capacity |
| CN103996843A (en) * | 2014-05-23 | 2014-08-20 | 桂林电子科技大学 | Porous lithium manganate nanosheet and preparation method thereof |
| CN103996843B (en) * | 2014-05-23 | 2016-04-20 | 桂林电子科技大学 | A kind of porous LiMn2O4 nanometer sheet and preparation method thereof |
| CN106146905A (en) * | 2016-08-01 | 2016-11-23 | 云南大学 | A kind of preparation method of half-natural material artificial carbon source material |
| CN106698383A (en) * | 2017-01-20 | 2017-05-24 | 中天储能科技有限公司 | Method of preparing lithium iron phosphate material by using coconut fibers |
| CN106698383B (en) * | 2017-01-20 | 2018-10-16 | 中天储能科技有限公司 | A method of LiFePO 4 material is prepared using coir fibre |
| CN115020659A (en) * | 2022-01-21 | 2022-09-06 | 昆明理工大学 | LiFePO 4 Preparation method of/C composite positive electrode material |
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