CN103400986A - Preparation method of lithium iron phosphorus oxide - Google Patents
Preparation method of lithium iron phosphorus oxide Download PDFInfo
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- CN103400986A CN103400986A CN2013103455216A CN201310345521A CN103400986A CN 103400986 A CN103400986 A CN 103400986A CN 2013103455216 A CN2013103455216 A CN 2013103455216A CN 201310345521 A CN201310345521 A CN 201310345521A CN 103400986 A CN103400986 A CN 103400986A
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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
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a preparation method of lithium iron phosphorus oxide. The preparation method comprises the steps: adding slow-soluble ferric citrate and insoluble ferric orthophosphate into an aqueous solution containing lithium hydroxide and a carbon source, to form a polyethylene glycol colloidal solution containing lithium ions, phosphate groups, ferric phosphate and ferric hydroxide, and after drying, carrying out calcination treatment to obtain the lithium iron phosphorus oxide material. The preparation method has the advantages of simple and easily controllable process and easy industrialized production. The prepared lithium iron phosphorus oxide has high tap density; and when being used as a positive electrode material of a lithium ion battery, the prepared lithium iron phosphorus oxide has the advantages of high compacted density, excellent processability, high capacity, excellent cycle performance and the like.
Description
Technical field
The present invention relates to lithium ion anode material, especially relate to a kind of preparation method of lithium iron phosphate oxide.
Background technology
Lithium ion battery, because of advantages such as its voltage is high, energy density large, long service life, has just been popularized rapidly since coming out, be widely used in portable type electronic product, electric tool, the aspects such as electric vehicle.Positive electrode is the important component part of lithium ion battery, account for more than 30% of whole battery cost, in charge and discharge process, positive electrode not only will be provided in positive and negative lithium intercalation compound the needed lithium of back and forth embedding/take off, but also will undertake the negative material surface, form the needed lithium of SEI film, therefore, the positive electrode of function admirable is the key point in the lithium ion battery industry development always.
At present, business-like anode material for lithium-ion batteries has LiCoO
2, LiMn
2O
4, LiFePO
4With ternary material etc., every kind of material property is different separately with price, the LiFePO4 that wherein has olivine structural, because its raw material sources are abundant, cost is low, environmental friendliness, the advantages such as security performance is high, specific capacity is high, discharge platform is steady, thermal stability and cycle performance excellence, be considered to the first-selection of electrokinetic cell.The raw material that prepare the LiFePO 4 material needs mostly are two or more, and each raw material are all solid powder, and how each raw material being mixed is to affect one of stable key issue of LiFePO 4 material.At present; lithium iron phosphate preparation method mostly adopts high temperature solid-state method; mix general solid ball milling or the solid-alcohol ball milling of adopting early stage; these methods can only guarantee that each stock yard reaches the mixing of micron level; while especially adopting ferric orthophosphate as raw material; the mixing meeting of this degree directly affects the reducing degree of trivalent iron salt, thereby affects specific capacity, processing characteristics and the cycle performance etc. of LiFePO4 final products, therefore limited the large-scale production of LiFePO 4 material.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of lithium iron phosphate oxide, the lithium iron phosphate oxide tap density that adopts the method to prepare is high, while as anode material for lithium-ion batteries, using, compacted density is high, processing characteristics is good, capacity is high, cycle performance is excellent, the method technique is simple and easy to control simultaneously, is suitable for very much the mass industrial production.
For achieving the above object, the present invention can take following technical proposals:
The preparation method of lithium iron phosphate oxide of the present invention, comprise the steps:
The first step, lithium hydroxide is dissolved in deionized water, be mixed with the solution of 3-10 mol/L, according to every liter of solution, add 20-80 gram polyethylene glycol, the ratio that every moles of hydrogen lithia adds the 10-40g organic carbon source adds the polyethylene glycol of weighing and organic carbon source in the lithium hydroxide solution for preparing, be heated to 60-90 ℃, be stirred to solid and dissolve fully, be mixed with lithium salt solution stand-by;
Second step: mixing source of iron and the phosphorus source of ferric orthophosphate and slow dissolubility ironic citrate preparation are dropped in the above-mentioned lithium salt solution for preparing successively, make the mol ratio of lithium and iron in solution reach 1.05: 1.0, be continuously stirring to abundant mixing, reaction, generate the colloidal solution that contains lithium ion, phosphate radical, ferric phosphate and iron hydroxide;
The 3rd step: the colloidal solution oven dry by prepared by second step, under inert gas shielding, be warming up to 300 ℃ of-800 ℃ of sintering 5-20 hour, after pulverizing, can obtain lithium iron phosphate oxide finished product.
Described organic carbon source comprises a kind of in glucose, sucrose; In described mixing source of iron, the weight percent proportioning of ferric orthophosphate and slow dissolubility ironic citrate is 4:1 ~ 2:1; Described phosphorus source is one or more in ferric orthophosphate, MAP, phosphoric acid.
Described inert gas comprises one or more in nitrogen, argon gas and hydrogen.
The invention has the advantages that and in liquid phase mixed process, adopted ironic citrate and two kinds of materials of ferric orthophosphate as source of iron early stage, ironic citrate wherein is a kind of slow soluble substance, with water miscible lithium hydroxide, form ferric hydroxide colloid, insoluble ferric orthophosphate is dispersed in colloid uniformly, contains lithium ion
Polyethylene glycolColloidal sol is enclosed in the surface of ferric phosphate uniformly, makes each raw material in solution, reach the mixability of ionic level; This mixed method can make the mixture homogeneity of raw material be greatly improved on the one hand, and the method for mixing in solution on the other hand has good repeatability, is more suitable for producing in batches; Once sintered method is adopted in firing of later stage, can reduce energy consumption, shorten sintering time, increases the output in the unit interval.
Embodiment
Lithium iron phosphate oxide finished product of the present invention can be described further by following embodiment.
Embodiment 1:
Take the lithium hydroxide of 13.57 grams, be dissolved in the deionized water of 50ml, add the glucose of 2.83 grams and the polyethylene glycol of 1.94 grams, be heated to 60-90 ℃, be stirred to solid and dissolve fully;
Take the ferric orthophosphate of 50 grams, the MAP of the ironic citrate of 12.5 grams and 6.79 grams, join in above-mentioned solution successively, stirs and generate the colloidal solution that contains lithium ion, phosphate radical, ferric phosphate and iron hydroxide;
By the oven dry of above-mentioned colloidal solution, under argon shield, be warming up to 720 ℃ of sintering 10 hours, sintered products is obtained to finished product after by ball mill grinding.After tested, the finished product tap density is 1.18 g/cm
3, make the lithium ion battery test: the pole piece compacted density is 2.36g/cm
3, gram volume is 162mAh/g (0.2C), 100 times the circulation volume conservation rate is 97.8%.
Embodiment 2:
Take the lithium hydroxide of 15.03 grams, be dissolved in the deionized water of 70ml, add the sucrose of 1.78 grams and the polyethylene glycol of 2.77 grams, be heated to 60-90 ℃, be stirred to solid and dissolve fully;
Take the ferric orthophosphate of 50 grams, the phosphoric acid of the ironic citrate of 21.42 grams and 10.53 grams, join in above-mentioned solution successively, stirs and generate the colloidal solution that contains lithium ion, phosphate radical, ferric phosphate and iron hydroxide;
By the oven dry of above-mentioned colloidal solution, under nitrogen protection, be warming up to 650 ℃ of sintering 15 hours, sintered products is obtained to finished product after by ball mill grinding.After tested, the finished product tap density is 1.22 g/cm
3, make the lithium ion battery test: the pole piece compacted density is 2.30g/cm
3, gram volume is 158mAh/g (0.2C), 100 times the circulation volume conservation rate is 98.6%.。
Embodiment 3:
Take 15.49 gram lithium hydroxides, be dissolved in the deionized water of 100ml, add the glucose of 1.46 grams and the polyethylene glycol of 3.44 grams, be heated to 60-90 ℃, be stirred to solid and dissolve fully;
Take the ferric orthophosphate of 50 grams, the phosphoric acid of the ironic citrate of 25 grams and 12.01 grams, join in above-mentioned solution successively, stirs and generate the colloidal solution that contains lithium ion, phosphate radical, ferric phosphate and iron hydroxide;
By the oven dry of above-mentioned colloidal solution, under the hybrid protection gas of nitrogen and hydrogen, be warming up to 800 ℃ of sintering 6 hours, sintered products is obtained to finished product after by ball mill grinding.After tested, the finished product tap density is 1.17g/cm
3, make the lithium ion battery test: the pole piece compacted density is 2.31g/cm
3, gram volume is 160mAh/g (0.2C), 100 times the circulation volume conservation rate is 98.3%.
Claims (3)
1. the preparation method of a lithium iron phosphate oxide, is characterized in that comprising the steps:
The first step, lithium hydroxide is dissolved in deionized water, be mixed with the solution of 3-10 mol/L, according to every liter of solution, add 20-80 gram polyethylene glycol, the ratio that every moles of hydrogen lithia adds the 10-40g organic carbon source adds the polyethylene glycol of weighing and organic carbon source in the lithium hydroxide solution for preparing, be heated to 60-90 ℃, be stirred to solid and dissolve fully, be mixed with lithium salt solution stand-by;
Second step: mixing source of iron and the phosphorus source of ferric orthophosphate and slow dissolubility ironic citrate preparation are dropped in the above-mentioned lithium salt solution for preparing successively, make the mol ratio of lithium and iron in solution reach 1.05: 1.0, be continuously stirring to abundant mixing, reaction, generate the colloidal solution that contains lithium ion, phosphate radical, ferric phosphate and iron hydroxide;
The 3rd step: the colloidal solution oven dry by prepared by second step, under inert gas shielding, be warming up to 300 ℃ of-800 ℃ of sintering 5-20 hour, after pulverizing, can obtain lithium iron phosphate oxide finished product.
2. according to the preparation method of the described lithium iron phosphate oxide of claims 1, it is characterized in that: described organic carbon source comprises a kind of in glucose, sucrose; In described mixing source of iron, the weight percent proportioning of ferric orthophosphate and slow dissolubility ironic citrate is 4:1 ~ 2:1; Described phosphorus source is one or more in ferric orthophosphate, MAP, phosphoric acid.
3. according to the preparation method of the described lithium iron phosphate oxide of claims 1, it is characterized in that: described inert gas comprises one or more in nitrogen, argon gas and hydrogen.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105206812A (en) * | 2015-09-24 | 2015-12-30 | 王海峰 | Method for preparing carbon-coated lithium iron phosphate through one-step hydrothermal method |
| CN115259130A (en) * | 2022-05-31 | 2022-11-01 | 中国科学院过程工程研究所 | Regeneration method of lithium iron phosphate reclaimed material and carbon-coated lithium iron phosphate material |
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| US5759717A (en) * | 1995-04-26 | 1998-06-02 | Japan Storage Battery Co., Ltd. | Method for manufacturing a positive electrode active material for lithium battery |
| CN101575093A (en) * | 2009-06-05 | 2009-11-11 | 郑州瑞普生物工程有限公司 | Preparation process of lithium iron phosphate material |
| CN101752562A (en) * | 2009-12-31 | 2010-06-23 | 惠州亿纬锂能股份有限公司 | Compound doped modified lithium ion battery anode material and preparation method thereof |
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2013
- 2013-08-09 CN CN2013103455216A patent/CN103400986A/en active Pending
Patent Citations (4)
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| US5759717A (en) * | 1995-04-26 | 1998-06-02 | Japan Storage Battery Co., Ltd. | Method for manufacturing a positive electrode active material for lithium battery |
| CN101575093A (en) * | 2009-06-05 | 2009-11-11 | 郑州瑞普生物工程有限公司 | Preparation process of lithium iron phosphate material |
| CN101575093B (en) * | 2009-06-05 | 2011-04-06 | 郑州瑞普生物工程有限公司 | Preparation process of lithium iron phosphate material |
| CN101752562A (en) * | 2009-12-31 | 2010-06-23 | 惠州亿纬锂能股份有限公司 | Compound doped modified lithium ion battery anode material and preparation method thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105206812A (en) * | 2015-09-24 | 2015-12-30 | 王海峰 | Method for preparing carbon-coated lithium iron phosphate through one-step hydrothermal method |
| CN105206812B (en) * | 2015-09-24 | 2017-09-22 | 王海峰 | The method that one step hydro thermal method prepares carbon coating type LiFePO4 |
| CN115259130A (en) * | 2022-05-31 | 2022-11-01 | 中国科学院过程工程研究所 | Regeneration method of lithium iron phosphate reclaimed material and carbon-coated lithium iron phosphate material |
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Application publication date: 20131120 |