CN102390824B - Preparation method of lithium iron phosphate - Google Patents
Preparation method of lithium iron phosphate Download PDFInfo
- Publication number
- CN102390824B CN102390824B CN 201110231947 CN201110231947A CN102390824B CN 102390824 B CN102390824 B CN 102390824B CN 201110231947 CN201110231947 CN 201110231947 CN 201110231947 A CN201110231947 A CN 201110231947A CN 102390824 B CN102390824 B CN 102390824B
- Authority
- CN
- China
- Prior art keywords
- phosphate
- iron
- salt
- soluble
- lithium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to a preparation method of lithium ion phosphate. The method comprises the following steps of: preparing an iron phosphate salt precursor by utilizing reverse precipitation of soluble iron salts and phosphate; cladding the ion phosphate salt precursor by using a surfactant; and then mixing with a lithium source and roasting together to prepare a carbon-doped LiFePO4 powder material with evenly distributed particles and small particle size. The preparation method disclosed by the invention has the advantages of low reaction temperature, mild reaction conditions, short technological flow, simple equipment requirement, environment friendliness and the like.
Description
Technical field
The invention belongs to technical field of lithium ion, be specifically related to a kind of method for preparing iron lithium phosphate.
Background technology
Iron lithium phosphate has that specific storage is high, good cycle, stable electrochemical property, lower-price characteristic, is first-selected dynamic lithium battery material of new generation.
Reported the iron lithium phosphate with olivine structural reversibly since the doff lithium from nineteen nineties, the research of iron lithium phosphate is more and more.
At present, the main preparation method of iron lithium phosphate has following several:
1, high temperature solid-state method, namely the compound of molysite, lithium and phosphoric acid salt mix, and react to obtain under hot environment.The product of the method preparation is because poorly conductive causes performance not good, and particle diameter is thick, and size distribution is inhomogeneous.As with as described in the Publication about Document:
1) Padhi A K, Nanjundaswamy K S, Masquelier C etc., Phospho-olivines as positive-elect rode materials for rechargeable lithiumbatteries.Electro-chemical Soc., 1997,144 (4), 1188-94.
2) Wang G X, Bewlaya S L, Konstantinov K etc., Physical andelectrochemical properties of doped lithium iron phosphate electrodes.Electrochimica Acta, 2004,50:443-7.
3) Prosini P P, Lisi M, Zane D etc., Determination of the chemicaldiffusion coeficient of lithium in LiFePO
4.Solid State lonics, 2002,148:3517-23.
4) Li Faxi, Chou Weihua, Hu Huanyu etc., microwave synthesizes anode material of lithium battery LiFePO chemical property, research and design, 2005,29 (6): 346-8.
5) Iriyama Y, Yokoyama M, Yada C etc., Preparation of LiFePO
4Thinfilms by pulsed laser deposition and their electrochemical properties[J] .Electrochem.SolidState Lett., 2004,7 (10): A340-2.
6) Sauvage F, Baudrin E, Gengembre L etc., Efect oftexture on theelectrochemical properties of LiFePO
4Thin films.Solid State lonics, 2005,176:1869-76.
2, carbothermic method is namely carried out high temperature reduction to the ferric iron source of cheapness.Although the method has overcome the shortcoming of molysite prices of raw and semifnished materials costlinesses, but still exist regional area carbon deposit storage larger, the problem of unstable product quality.As with as described in the Publication about Document:
7) Mich H, Cao G S, Zhao X B etc., Low-cost, one-step process forsynthesis of carbon-coated LiFePO
4Cathode.Materials Letters, 2005,59:127-30.
8) open treasured, Li Xinhai, ZhuBing Quan, etc. precipitation carbothermic reduction integrated process prepares the peridotites iron lithium phosphate. China YouSe Acta Metallurgica Sinica, 2006,16 (8): 1445-9.
3, sol-gel method take ferric acetate or nitrate as raw material, is mixed lithium hydroxide, citric acid, phosphoric acid, making 60 ℃ of lower reactions.Although the method temperature of reaction is lower, the product shrinkability is large when drying, is only suitable in the short run experiment, and large batch of suitability for industrialized production difficulty is larger, and synthesis cycle is longer.As with as described in the Publication about Document:
9) Sang Junli, Wang Qiaojuan, Guo Xifeng. the synthetic and characterization technique of lithium iron phosphate positive material. inorganic chemicals industry, 2008,40 (2): 13-6.
10) Croce F, Ep ifanio A D etc., A novel concept for the synthesis ofan improved LiFePO
4Lithium battery cathode.Electrochem Solid StateLett., 2002,5 (3): A47-50.
4, the precipitator method prepare first phosphoric acid molysite precursor, more at a certain temperature roasting.This method is more a kind of method of using at present.But the problem that exists is because the electroconductibility of iron lithium phosphate own is relatively poor, need to mixes conductive carbon material when post-processed, thereby significantly reduce the tap density of material.Therefore the battery volume of making will be very huge, be difficult to obtain practical application.As with as described in the Publication about Document:
11) Han Enshan, Feng Zhihui, Wei Zihai etc., coprecipitation method synthesizing iron lithium phosphate carbon dope composite positive pole. inorganic chemicals industry, 2008,40 (1): 22-5.
12) Li Jun, Zheng Yuying, Li Daguang etc., the preparation of novel high-energy-density iron lithium phosphate and chemical property. material Leader, 2008,22 (4): 138-9.
Except above-mentioned shortcoming, also there is following deficiency in existing method: at LiFePO
4In the structure, because the PO between the octahedron
4Tetrahedron has limited the variation of lattice volume, affect the Li atom in charge and discharge process embedding and deviate from, make LiFePO
4The ion rate of diffusion lower; Owing to there not being continuous FeO
6The octahedra network in limit can not form electronic conductor altogether, and the conduction of electronics can only be undertaken by Fe-O-Fe, makes LiFePO
4Electronic conductivity lower.
Summary of the invention
The technical problem to be solved in the present invention is how to improve the specific conductivity of iron lithium phosphate.
In order to solve the problems of the technologies described above, the invention provides a kind of method for preparing iron lithium phosphate.
The method that the present invention prepares iron lithium phosphate may further comprise the steps: soluble ferric iron salt and soluble phosphate reverse precipitation are prepared tertiary iron phosphate salt precursor body; coat gained tertiary iron phosphate salt precursor body with containing carbon surface active agent; then be blended in roasting in the atmosphere of shielding gas with the lithium source, obtain the LiFePO of carbon dope
4Powder.
Wherein, described soluble ferric iron salt is selected from FeSO
4, FeCl
2, Fe
2(SO
4)
3, Fe (NO
3)
3, Fe (NO
3)
2And FeCl
3In one or more; Preferred FeSO
4
In the raw material soluble ferric iron salt of the present invention, can add separately divalence or trivalent iron salt, but when adopt adding the mixture of divalence and trivalent iron salt, can make product property better.
Described soluble phosphate is selected from NH
4H
2PO
4, (NH
4)
2HPO
4, (NH
4)
3PO
4, LiH
2PO
4, Li
2HPO
4, Li
3PO
4, KH
2PO
4, K
2HPO
4, K
3PO
4, NaH
2PO
4, Na
2HPO
4And Na
3PO
4In one or more; Preferably phosphoric acid ammonium salt and phosphoric acid lithium salts, because its technological process is simpler, lithium salts particularly, effect is best; More preferably NH
4H
2PO
4Also can adopt sylvite or sodium salt, but washing process is slightly more complex.
Described soluble ferric iron salt needs slowly to add in the soluble phosphoric acid salts solution, can improve combination rate; If the adding excessive velocities then can cause reacting insufficient.
The described carbon surface active agent that contains is selected from C
10～C
20In carboxylic acid or the carboxylate salt one or more; Preferred C
14～C
18In the carboxylic acid one or more are such as oleic acid, linolic acid etc.; The more preferably C of better effects if
14～C
18The solubility carboxylate salt is such as C
14～C
18Carboxylic acid lithium or carboxylic acid ammonium.
The described effect that contains carbon surface active agent is that uniform particles is distributed, and as carbon source.In addition, when soluble ferric iron salt adopted trivalent iron salt, containing carbon surface active agent in reaction process can also be reduced to ferrous iron with ferric iron, can evenly be attached to the product surface, thereby improved the electroconductibility of product, avoided carbon deposit to deposit, and promoted Li
+Deviate from and embed, improve electronic conductivity.
The weight that contains carbon surface active agent that the present invention is used is 10%～60% of described tertiary iron phosphate salt precursor body; Preferred 10～25%; More preferably 25%.But optimal addn also depends on washing process.If the raw material that adopts is nitrate, the add-on of tensio-active agent can be lacked, and when adopting vitriol or muriate raw material, the add-on of tensio-active agent is slightly more.
But this optimal addn also depends on washing process.If the raw material that adopts is the nitrate of iron, the add-on that contains carbon surface active agent can be lacked, such as 10～20%; And when adopting the vitriol of iron or muriate to be raw material, the add-on that contains carbon surface active agent can be more more, such as 40～60%.
Described lithium source is selected from Li
3PO
4, Li
2CO
3, LiOH and CH
3Among the COOLi one or more; Preferred Li
2CO
3More preferably Li
3PO
4As adopt when precipitating Trilithium phosphate as precipitation agent, and it can use as lithium source and precipitation agent simultaneously, and technological process is easy, can also reduce the add-on of tensio-active agent.
Described shielding gas is nitrogen or argon gas.
The temperature of described roasting is 400～1200 ℃, preferred 800～1000 ℃, and more preferably 800 ℃.
The time of described roasting is 2～20h, preferred 12～15h, more preferably 15h.
Maturing temperature and time are then depended on the product cut size of needs, and required particle diameter hour can adopt the long-time sinter process of low temperature; And when requiring size distribution narrower, can adopt sinter process between high temperature, short time.Maturing temperature and time are also depended on the amount of each calcination product, and amount is many, and temperature is higher, and the time is correspondingly longer.
The mol ratio in soluble ferric iron salt, soluble phosphate, lithium source is very crucial to product performance, and their molar ratio range is (1～3): (2～6): 1; Preferred mol ratio is 2: 4: 1.According to producing actual needs, the mol ratio of these three kinds of raw materials can also be regulated according to the raw material type that adopts, the factors such as processing parameter of preparation.
For the different application field of iron lithium phosphate, fields such as battery of mobile phone, power cell, energy-accumulating power station on the basis of the inventive method, in scope disclosed by the invention, by changing various parameters, can obtain the product of different electro-chemical properties; In the raw material soluble ferric iron salt, can add separately divalence or trivalent iron salt, but performance is better when adopt adding the mixture of divalence and trivalent iron salt.The anion species of raw material source of iron is not very large to the performance impact of product, but production process is had certain influence, and is as simpler with nitrate technique, slightly more complex during with vitriol and muriate.But from the raw materials cost angle, vitriol and muriate have more advantage undoubtedly.
Beneficial effect of the present invention is as follows.
1. the present invention adopts soluble ferric iron salt to prepare even particle distribution, the surperficial LiFePO that coats the small particle size of one deck carbon nanometer layer with the standby phosphoric acid molysite of soluble phosphate reverse precipitation legal system, precipitation by the three-step approach that contains carbon surface active agent parcel, the source roasting of remix lithium
4Powdered material.
2. method of the present invention has all advantages of reverse precipitation method, prepared LiFePO
4Powdered material good dispersity, even particle size distribution.
3. parcel contains carbon surface active agent in preparation process, and its Main Function is as follows: (1) has promoted the even distribution of particle better; (2) as carbon source, in roasting process, do not need again to add carbon source; (3) when soluble ferric iron salt adopts trivalent iron salt, in reaction process, ferric iron is reduced to ferrous iron, and can improves product electric conductivity, promote Li
+Deviate from and embed; (4) nano-carbon layer that evenly coats can greatly improve LiFePO
4The chemical property of positive electrode material causes the reduction of the inhomogeneous and material stacking density of carbon dope when simultaneously having avoided again the ordinary method carbon dope.
4. the characteristics such as to have temperature of reaction low for method of the present invention, and reaction conditions is gentle, and the short and equipment requirements of technical process is simple.In preparation process, do not adopt toxic substance, environmental protection, the little and homogeneous of the product granularity of preparation.
5. the LiFePO of method of the present invention preparation
4Because particle diameter is little, particle surface is even, Li
+The diffusion distance shorten, promoted Li
+Embedding and deviate from, improved LiFePO
4The ion rate of diffusion, make product have preferably chemical property, can improve LiFePO
4Electronic conductivity 10～50%.It is high that this material has specific storage, good cycle, stable electrochemical property, lower-price characteristic.The prepared iron lithium phosphate product of the present invention can be used as power lithium-ion battery positive electrode material of new generation.
Embodiment
Following examples are used for explanation the present invention, but are not used for limiting the scope of the invention.
Embodiment 1
With ferrous sulfate (FeSO
47H
2O, analytical pure) be source of iron, ammonium di-hydrogen phosphate (NH
4H
2PO
4) be the phosphorus source, Li
2CO
3Be the lithium source.Get FeSO
47H
2O 5.558g is dissolved in 20ml deionized water, NH
4H
2PO
44.6g be dissolved in the 20ml deionized water, filter, copperas solution is slowly splashed in the biphosphate ammonia solution, generate NH
4FePO
4The presoma precipitation is filtered, and washing is at 80 ℃ of lower dry 24h; Then presoma is dissolved under ultrasound condition in the ethanolic soln of oil-containing acid surfaces promoting agent, the oleic acid consumption is 25% of presoma quality, filters drying; Get Li
2CO
30.74g ball milling descends and the tertiary iron phosphate salt precursor body constant temperature calcining 15h (N that is coated by tensio-active agent at 800 ℃
2Atmosphere), cooling namely obtains LiFePO
4Positive electrode material.FeSO in the present embodiment
47H
2O: NH
4H
2PO
4: Li
2CO
3Between mol ratio be 2: 4: 1.
Embodiment 2
With iron nitrate and Iron nitrate (Fe (NO
3)
39H
2O and Fe (NO
3)
26H
2O, analytical pure) be source of iron, potassium primary phosphate (KH
2PO
4) be the phosphorus source, LiOH is the lithium source.Get respectively Fe (NO
3)
3And Fe (NO
3)
26.06g and 2.70g is dissolved in 30ml deionized water, KH
2PO
48.16g be dissolved in the 30ml deionized water, filter, iron nitrate and ferrous nitrate solution are slowly splashed in the potassium dihydrogen phosphate, generate KFePO
4The presoma precipitation is filtered, and washing is at 80 ℃ of lower dry 24h; Then presoma is dissolved under ultrasound condition in the ethanolic soln that contains ammonium oleate, the ammonium oleate consumption is 10% of presoma quality, filters drying; Get LiOH 0.24g, ball milling descends and the tertiary iron phosphate salt precursor body constant temperature calcining 7h (N that is coated by tensio-active agent at 1200 ℃
2Atmosphere), cooling namely obtains LiFePO
4Positive electrode material.Fe (NO in the present embodiment
3)
3: Fe (NO
3)
2: KH
2PO
4: the mol ratio between LiOH is 1.5: 1.5: 6: 1.
Embodiment 3
With iron(ic) chloride (FeCl
3, analytical pure) and be source of iron, Trilithium phosphate (Li
3PO
4) be the phosphorus source, LiOH is the lithium source.Get FeCl
31.62g be dissolved in the 20ml deionized water, Li
3PO
42.32g be dissolved in the 20ml deionized water, filter, ferric chloride Solution is slowly splashed in the Trilithium phosphate solution, generate LiFePO
4The presoma precipitation is filtered, and washing is at 90 ℃ of lower dry 20h; Then presoma is dissolved under ultrasound condition and contains in the linoleic ethanolic soln, the linolic acid consumption is 40% of presoma quality, filters drying; Get LiOH 0.24g, ball milling, with the tertiary iron phosphate salt precursor body constant temperature calcining 20h (argon gas atmosphere) that is coated by tensio-active agent, cooling namely obtains LiFePO under 400 ℃
4Positive electrode material.FeCl in the present embodiment
3: Li
3PO
4: the mol ratio between LiOH is 1: 2: 1.
The product that present method obtains is compared with ordinary method, and granule-morphology is subglobular more, and good fluidity, processability are good; Grain diameter can reduce more than 20%, and size distribution is narrower.When the products obtained therefrom powder was made battery, tap density improved 5～15% than ordinary method.As with the 1.3-1.5g/cm of ordinary method
3Compare, the product tap density of present method preparation can reach 1.6-1.8g/cm
3
Although above the present invention is described in detail with a general description of the specific embodiments, on basis of the present invention, can make some modifications or improvements it, this will be apparent to those skilled in the art.Therefore, these modifications or improvements all belong to the scope of protection of present invention without departing from theon the basis of the spirit of the present invention.
Claims (8)
1. method for preparing iron lithium phosphate; it is characterized in that; may further comprise the steps: soluble ferric iron salt and soluble phosphate reverse precipitation are prepared tertiary iron phosphate salt precursor body; coat gained tertiary iron phosphate salt precursor body with containing carbon surface active agent; then be blended in roasting in the shielding gas atmosphere with the lithium source, obtain the LiFePO of carbon dope
4Powder;
Wherein, described soluble ferric iron salt needs slowly to add in the soluble phosphoric acid salts solution;
The described carbon surface active agent that contains is selected from C
10～C
20In carboxylic acid or the carboxylate salt one or more;
The mol ratio in described soluble ferric iron salt, soluble phosphate, lithium source is 1～3:2～6:1.
2. method according to claim 1 is characterized in that, described soluble ferric iron salt is selected from FeSO
4, FeCl
2, Fe
2(SO
4)
3, Fe (NO
3)
3, Fe (NO
3)
2And FeCl
3In one or more.
3. method according to claim 1 is characterized in that, described soluble phosphate is selected from NH
4H
2PO
4, (NH
4)
2HPO
4, (NH
4)
3PO
4, LiH
2PO
4, Li
2HPO
4, Li
3PO
4, KH
2PO
4, K
2HPO
4, K
3PO
4, NaH
2PO
4, Na
2HPO
4And Na
3PO
4In one or more.
4. method according to claim 1 is characterized in that, the described weight that contains carbon surface active agent is 10%～60% of described tertiary iron phosphate salt precursor body.
5. method according to claim 1 is characterized in that, described lithium source is selected from Li
3PO
4, Li
2CO
3, LiOH and CH
3Among the COOLi one or more.
6. method according to claim 1 is characterized in that, described shielding gas is nitrogen or argon gas.
7. method according to claim 1 is characterized in that, the temperature of described roasting is 400～1200 ℃.
8. method according to claim 1 is characterized in that, the time of described roasting is 2～20h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110231947 CN102390824B (en) | 2011-08-10 | 2011-08-10 | Preparation method of lithium iron phosphate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110231947 CN102390824B (en) | 2011-08-10 | 2011-08-10 | Preparation method of lithium iron phosphate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102390824A CN102390824A (en) | 2012-03-28 |
| CN102390824B true CN102390824B (en) | 2013-02-20 |
Family
ID=45858235
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201110231947 Expired - Fee Related CN102390824B (en) | 2011-08-10 | 2011-08-10 | Preparation method of lithium iron phosphate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102390824B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9660267B2 (en) * | 2009-09-18 | 2017-05-23 | A123 Systems, LLC | High power electrode materials |
| ITTO20120709A1 (en) * | 2012-08-07 | 2014-02-08 | Fond Istituto Italiano Di Tecnologia | PROCEDURE OF COLLOIDAL SYNTHESIS OF LITHIUM FOSFATE IRON |
| CN104973582A (en) * | 2014-04-03 | 2015-10-14 | 南京工业大学 | Synthesis method of novel ion battery anode material iron phosphate |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101546826A (en) * | 2009-04-30 | 2009-09-30 | 宁波职业技术学院 | Preparation method for spherical lithium ferric phosphate used as lithium ion battery anode material |
| CN101656311A (en) * | 2009-09-17 | 2010-02-24 | 复旦大学 | Preparation method of LiFePO4/C composite material |
| CN102034964A (en) * | 2009-09-24 | 2011-04-27 | 复旦大学 | Method for preparing lithium ion battery composite material |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011057646A1 (en) * | 2009-11-10 | 2011-05-19 | Rockwood Italia S.P.A. | Hydrothermal process for the production of lifepo4 powder |
-
2011
- 2011-08-10 CN CN 201110231947 patent/CN102390824B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101546826A (en) * | 2009-04-30 | 2009-09-30 | 宁波职业技术学院 | Preparation method for spherical lithium ferric phosphate used as lithium ion battery anode material |
| CN101656311A (en) * | 2009-09-17 | 2010-02-24 | 复旦大学 | Preparation method of LiFePO4/C composite material |
| CN102034964A (en) * | 2009-09-24 | 2011-04-27 | 复旦大学 | Method for preparing lithium ion battery composite material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102390824A (en) | 2012-03-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zhang et al. | One-step microwave synthesis and characterization of carbon-modified nanocrystalline LiFePO4 | |
| Bi et al. | Self-assembled flower-like structure of copper cobaltate nanosheets supported on nitrogen-doped carbon nanofibers as functional electrocatalyst for lithium/polysulfides batteries | |
| CN105390674B (en) | A kind of two ferrous selenides of sodium-ion battery/sulfur doping graphene anode material and preparation method thereof | |
| Zou et al. | Mixed-carbon-coated LiMn0. 4Fe0. 6PO4 nanopowders with excellent high rate and low temperature performances for lithium-ion batteries | |
| CN101826617B (en) | Preparation method of lithium iron phosphate | |
| CN105576217B (en) | A kind of preparation method of the phosphate cathode material of three-dimensional carbon in-stiu coating | |
| Göktepe et al. | Effect of silver and carbon double coating on the electrochemical performance of LiFePO4 cathode material for lithium ion batteries | |
| CN107808958B (en) | Preparation method of ferroferric oxide/nitrogen-doped graphene composite material, product and application thereof | |
| Huang et al. | Reaction mechanisms on solvothermal synthesis of nano LiFePO4 crystals and defect analysis | |
| CN105428649A (en) | Nano-carbon coated sodium ferrous fluorophosphates and preparation method of hydrothermal method | |
| CN102244246B (en) | Preparation method of lithium iron phosphate/carbon composite material | |
| CN102104143A (en) | Hydrothermal synthesis method of composite material for high-performance power battery | |
| CN101964411A (en) | LiFePO4 composite type positive pole material and preparation method thereof | |
| Li et al. | MOF-derived Al-doped Na2FePO4F/mesoporous carbon nanonetwork composites as high-performance cathode material for sodium-ion batteries | |
| Yoon et al. | Effect of synthesizing method on the properties of LiFePO 4/C composite for rechargeable lithium-ion batteries | |
| Meng et al. | Scalable synthesis of Ti3+ self-doped Li4Ti5O12 microparticles as an improved performance anode material for Li-ion batteries | |
| Li et al. | Tuning the electrochemical behaviors of N-doped LiMnxFe1–xPO4/C via cation engineering with metal–organic framework-templated strategy | |
| CN104600303A (en) | Preparation method of nano lithium iron phosphate positive electrode material | |
| Örnek et al. | Improving the cycle stability of LiCoPO4 nanocomposites as 4.8 V cathode: Stepwise or synchronous surface coating and Mn substitution | |
| Hou et al. | Highly [010]-oriented self-assembled LiCoPO 4/C nanoflakes as high-performance cathode for lithium ion batteries | |
| CN102390824B (en) | Preparation method of lithium iron phosphate | |
| CN106169567A (en) | A kind of lithium iron phosphate positive material of carbon cladding and preparation method thereof | |
| Nallathamby et al. | Carbonate anion controlled growth of LiCoPO4/C nanorods and its improved electrochemical behavior | |
| Liu et al. | Improving the electrochemical performance of single crystal LiNi0. 5Mn1. 5O4 cathode materials by Y–Ti doping and unannealing process | |
| CN102544494A (en) | Preparation method of nano composite lithium iron phosphate cathode material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20200831 Address after: 211100 No. 1 Dongji Avenue, Jiangning District, Nanjing City, Jiangsu Province (Jiangning Development Zone) Patentee after: Nanjing Hongyi Botai Digital Technology Co.,Ltd. Address before: 314400 Zhejiang province Haining City Double Road No. 128 branch center one building 2 floor East Patentee before: Zhu Xuguo |
|
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20130220 Termination date: 20210810 |