CN101935028B - Preparation method of nano lithium iron phosphate with high tap density - Google Patents
Preparation method of nano lithium iron phosphate with high tap density Download PDFInfo
- Publication number
- CN101935028B CN101935028B CN201010293132XA CN201010293132A CN101935028B CN 101935028 B CN101935028 B CN 101935028B CN 201010293132X A CN201010293132X A CN 201010293132XA CN 201010293132 A CN201010293132 A CN 201010293132A CN 101935028 B CN101935028 B CN 101935028B
- Authority
- CN
- China
- Prior art keywords
- iron phosphate
- preparation
- lithium iron
- tap density
- solution
- 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
Images
Classifications
-
- 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
Landscapes
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a preparation method of nano lithium iron phosphate with high tap density, which is characterized by comprising the following steps of: (1) primary granulation: dissolving soluble ferrite and phosphoric acid in deionized water, adding a complexing agent and slowly adding a lithium salt solution while stirring continuously; (2) continuously stirring the solution in an oil bath until green precipitate is produced, filtering by pumping, and washing to obtain solid products; (3) drying the solid products in vacuum, and pulverizing by ball milling to obtain precursor powder; (4) dissolving the precursor powder and organic carbon in deionized water, fully stirring and mixing, and drying in vacuum to obtain standby precursor powder; (5) secondary granulation: stirring the product of the primary granulation in a vacuum container for granulation until the material becomes semi-dry particles; and (6) firstly drying the granulated powder in a vacuum drying box, and then sintering under the protection of inert atmosphere to obtain spherical lithium iron phosphate with micron particle size. The transmission rate of ions and electrons can be increased by nanosizing the lithium iron phosphate, and the conductive property of the lithium iron phosphate is further improved.
Description
Technical field
The invention belongs to the green energy resource field of materials, be a kind of anode material for lithium-ion batteries technology of preparing, particularly a kind of preparation method of high tap density nano-grade lithium iron phosphate.
Background technology
In lithium ion battery, positive electrode material is its most important component, also is the key of decision lithium ion battery performance.At present, main positive electrode material is LiCoO
2, LiNiO
2, LiMn
2O
4Wherein, LiCoO
2Be unique industrialization on a large scale at present, commercial positive electrode material, 90% above lithium ion battery adopts this material.But employed Co costs an arm and a leg in this material, and capacity is lower, and toxicity is bigger, has certain safety issue.LiNiO
2Cost is lower, and capacity is higher, but the preparation difficulty, and there is bigger potential safety hazard in poor heat stability.Spinel LiMn
2O
4Cost is low, and security is good, but capacity is low, and high temperature cyclic performance is poor.Therefore need develop novel positive electrode material satisfies the growing market requirement.
Characteristics such as LiFePO 4 material has that security is good, cycle performance is excellent, environmental friendliness, raw material sources are extensive; Wherein, Lithium, iron, phosphorus all are the abundant elements of reserves on the earth, and especially the ferrous material raw material sources are wide, and are cheap; Be acknowledged as the first-selected positive electrode material of lithium ion battery of new generation, become the primary study and the developing direction of main developed country in the world today.And, because self and employed electrolytic solution are stable under its high temperature, and have the good high-temperature cycle performance, be particularly suitable for doing power cell.
Secondly, its relative Ni-H, the Ni-Cd battery has great advantage.Lithium iron phosphate dynamic battery has seven big advantages: one, extra long life.2000 circulation volume conservation rates are more than 80%.Two, safe in utilization; Iron lithium phosphate has solved the security hidden trouble of cobalt acid lithium and lithium manganate fully; Cobalt acid lithium and lithium manganate can produce blast down in the intensive collision human consumer's life security is constituted a threat to, even and iron lithium phosphate can not produce blast with the safety test of passing through strictness yet in worst traffic hazard.Three, electric current fast charging and discharging greatly, under special charger, the 1.5C charging can make battery be full of in 40 minutes, and starting current can reach 2C, and lead-acid cell does not then have this performance.Four, high temperature resistant, iron lithium phosphate electric heating peak value can reach 350 ℃～500 ℃ and cobalt acid lithium and lithium manganate about 200 ℃.Five, large vol.Six, memory-less effect.Seven, environmental protection.But the tap density of LiFePO4 positive electrode material is less, waits the volume of the ferric phosphate lithium cell of capacity to be greater than lithium ion batteries such as boring sour lithium, and its ion and electronic conductivity are not good, cause the charge-discharge magnification performance not good.These have all greatly influenced LiFePO
4Replace LiCoO
2Become anode material for lithium-ion batteries of new generation.
And mostly the preparation of present most of lithium iron phosphate positive materials is through solid phase method sintering preparation, again it is carried out carbon and coats; With the conductivity of increase iron lithium phosphate, and in fact, the iron lithium phosphate of solid phase method preparation promptly enables to reach smaller particle size; But carbon also can only be attached to micron-sized particle surface, and its inside still electroconductibility is relatively poor, and mostly the iron lithium phosphate that solid phase method is prepared small particle size is the method through fragmentation; And the particle diameter of gained is inhomogeneous on the one hand in the process of fragmentation; Efficient is lower, secondly also breaks the structure of ring material easily, thereby has determined that fundamentally its conductivity is relatively poor.
Summary of the invention
In order to solve above-mentioned existing problem, the purpose of this invention is to provide a kind of preparation method of high tap density nano-grade lithium iron phosphate.Through with the LiFePO 4 material nanometer, can improve the transmission rate of ion and electronics, thereby improve its conductivity.
The objective of the invention is to realize through following technical proposals; A kind of preparation method of high tap density nano-grade lithium iron phosphate is characterized in that, it is nanometer particle that described nano-grade lithium iron phosphate makes primary particle through the homogeneous phase crystallization process; Offspring is the micro-size particles of gained after granulation process; Be the primary particle nanometer, the offspring micronization, micron-sized particle is made up of many nano level particles.
Said acquisition primary particle nanometer, the method for offspring micronization may further comprise the steps:
1) carry out a granulation: according to mol ratio is that 1: 1 ratio takes by weighing soluble ferrite and phosphoric acid is dissolved in the deionized water; According to the mol ratio of complexing agent and iron ion is that 0.1: 1 ratio adds complexing agent; And under constantly stirring, according to phosphonium ion: iron ion: the lithium ion mol ratio is that 1: 1: 1～3 ratio slowly adds lithium salt solution;
2) above-mentioned solution is continued to stir 1～2h in 110～140 ℃ of oil baths; To producing green precipitate, green precipitate is carried out suction filtration, washing obtains solid product;
3) with the gained solid product in vacuum drying oven in 60～80 ℃ of drying 6～10h; Dried presoma carries out ball mill pulverizing, and obtaining particle diameter is the presoma powder of 30～100nm;
4) be that 1: 0.03～0.1 ratio is dissolved in the deionized water with gained presoma powder and organic carbon according to mass ratio, after fully mixing, place vacuum drying oven, obtain subsequent use presoma in 60～80 ℃ of drying 12～24h;
5) carry out secondary granulation: subsequent use precursor powder of gained and macromolecule polymer solution are put in the enclosed vacuum container, utilized the stirrer high-speed stirring; Simultaneously, the fog nozzle that is positioned at vacuum vessel top sprays the macromolecule polymer solution of subsequent use precursor powder weight 1%～10%, continues 1-4h, is half-dried granular to material, and particle diameter is at 10um～100um;
The powder that 6) will pass through after the granulation carries out sintering, earlier in vacuum drying oven in 60～80 ℃ of drying 5～8h, put into the inert atmosphere protection stove then, in 550 ℃～700 ℃ sintering 6～10h, promptly get the spheroid iron lithium phosphate of micron order particle diameter.
Described soluble ferrite is one or more in ferrous sulfate, iron protochloride or their hydrate.
The volumetric concentration of said phosphoric acid solution is 85%.
Said complexing agent is one or more of terepthaloyl moietie, trolamine.
Said lithium salt solution is one or more of Lithium Hydroxide MonoHydrate, Quilonum Retard, Lithium Sulphate or their hydrate.
Said organic carbon is one or more of sucrose, glucose, Hydrocerol A, Zusoplast 9002.
Described macromolecule polymer solution is one or more in Z 150PH, resol, glucose, sucrose, Vilaterm, the Vestolen PP 7052, the water-soluble or pure solution that is configured to, and strength of solution is 1%～10%.
The present invention is through adopting nano lithium iron phosphate material; Material is through the primary particle nanometer, and the nano level particle that the method for offspring micronization obtains makes a micron particle be made up of many nanometer particles; And there is the space to exist between the nanoparticle; Electrolytic solution enters into micron-sized spherical particles inside easily like this, is convenient to the ionic transmission, has increased conductivity greatly.
In addition, nanoparticle is carried out secondary granulation, make it reach micron order, and adopt process for granulating to obtain the iron lithium phosphate of different-grain diameter, mix, thereby improved tap density.Also make material in use just with operation.
Description of drawings
Fig. 1 is the XRD figure of the iron lithium phosphate for preparing among the embodiment.
Fig. 2 is the charging and discharging curve that positive electrode material is packaged into the 5C of battery among the embodiment 2.
Embodiment
Below in conjunction with embodiment the present invention is explained further details.
Embodiment 1
1) carries out a granulation: take by weighing the 1.5mol ferrous sulfate; 1.5mol phosphoric acid (effective content by 85% volumetric concentration phosphoric acid calculates) is dissolved in the deionized water of 3000ml, adds 0.15mol complexing agent terepthaloyl moietie; Constantly stir, slowly add the lithium hydroxide solution 4500ml of 1.5mol;
2) above-mentioned solution is continued to stir time 1h in 110 ℃ of oil baths; Produce green precipitate, green precipitate is carried out suction filtration, washing obtains solid product;
3) with the gained solid product in vacuum drying oven in 60 ℃ of dry 6h; Dried presoma carries out ball mill pulverizing, and obtaining particle diameter is 30nm presoma powder;
4) be that 1: 0.03 ratio is dissolved in the deionized water with gained presoma powder and organic carbon sucrose according to mass ratio, after fully mixing, place vacuum drying oven, obtain subsequent use presoma in 60 ℃ of temperature drying 12h;
5) carry out secondary granulation: subsequent use precursor powder of gained and macromolecule polymer solution are put in the enclosed vacuum container, utilized the stirrer high-speed stirring; Simultaneously; Spray the high molecular polymer polyvinyl alcohol solution of subsequent use precursor powder weight 1% to the fog nozzle that is positioned at vacuum vessel top, high molecular polymer polyvinyl alcohol solution concentration is 10% alcoholic solution, continues 1 hour; Be half-dried granular to material, particle diameter is at 10um;
The powder that 6) will pass through after the granulation carries out sintering: in vacuum drying oven, be 60 ℃ earlier in temperature, and dry 5 hours, put into the inert atmosphere protection stove then, in 550 ℃ of sintering 6 hours, promptly get the micron-sized spheroid iron lithium phosphate of particle diameter.
The present invention sees shown in Figure 1 through the XRD figure of the iron lithium phosphate of the foregoing description 1 preparation.
Embodiment 2
1) carries out a granulation: take by weighing the 1mol iron protochloride; 1mol phosphoric acid (effective content by 85% volumetric concentration phosphoric acid calculates) is dissolved in the deionized water of 2000ml, adds 0.1mol complexing agent terepthaloyl moietie and trolamine; Constantly stir, slowly add 2mol Quilonum Retard solution 4500ml;
2) above-mentioned solution is continued to stir time 2h in 140 ℃ of oil baths; Produce green precipitate, green precipitate is carried out suction filtration, washing obtains solid product;
3) with the gained solid product in vacuum drying oven in 80 ℃ of dry 10h, dried presoma carries out ball mill pulverizing, obtaining particle diameter is the presoma powder of 100nm;
4) be that 1: 0.1 ratio is dissolved in the deionized water with gained presoma powder and organic carbon glucose and Hydrocerol A according to mass ratio, after fully mixing, place vacuum drying oven, obtain subsequent use presoma in 80 ℃ of dry 18h;
5) carry out secondary granulation: subsequent use precursor powder of gained and macromolecule polymer solution are put in the enclosed vacuum container, utilized the stirrer high-speed stirring; Simultaneously; The fog nozzle that is positioned at vacuum vessel top sprays the high molecular polymer phenol resin solution into subsequent use precursor powder weight 10%, and high molecular polymer phenol resin solution concentration is 1% alcoholic solution, continues 4 hours; Be half-dried granular to material, particle diameter is at 100um;
The powder that 6) will pass through after the granulation carries out sintering, earlier in vacuum drying oven in 80 ℃ drying 8 hours, put into the inert atmosphere protection stove then, in 700 ℃ of sintering 10 hours, promptly get the spheroid iron lithium phosphate of micron order particle diameter.
The present invention sees shown in Figure 2 through the charging and discharging curve effect of the 5C of the anode sizing agent packaged battery of the foregoing description 2 preparations.Conductivity between this charging and discharging curve explanation slurry nanoparticle of the present invention is improved.
Embodiment 3
1) carries out a granulation: take by weighing 1.5mol ferrous sulfate and iron protochloride; 1.5mol phosphoric acid (effective content by 85% volumetric concentration phosphoric acid calculates); Be dissolved in the deionized water of 3000ml; Add 0.15mol complexing agent terepthaloyl moietie and trolamine, constantly stir, slowly add the lithium sulfate solution 4500ml of 1.5mol;
2) above-mentioned solution is continued to stir time 1.5h in 266 ° of F oil baths; Produce green precipitate, green precipitate is carried out suction filtration, washing obtains solid product;
3) with the gained solid product in vacuum drying oven in 70 ℃ of dry 8h; Dried presoma carries out ball mill pulverizing, and obtaining particle diameter is the presoma powder of 50nm;
4) be that 1: 0.06 ratio is dissolved in the deionized water with gained presoma powder and organic carbon sucrose, rock sugar and Hydrocerol A according to mass ratio, after fully mixing, place vacuum drying oven, obtain subsequent use presoma in 70 ℃ of dry 24h;
5) carry out secondary granulation: subsequent use precursor powder of gained and macromolecule polymer solution are put in the enclosed vacuum container, utilized the stirrer high-speed stirring; Simultaneously; Spray the high molecular polymer dextrose plus saccharose solution of subsequent use precursor powder weight 5% to the fog nozzle on vacuum vessel top, high molecular polymer dextrose plus saccharose strength of solution is 5% the aqueous solution, continues 2 hours; Be half-dried granular to material, particle diameter is at 50um;
The powder that 6) will pass through after the granulation carries out sintering, earlier in vacuum drying oven in 70 ℃ drying 6 hours, put into the inert atmosphere protection stove then, in 600 ℃ of sintering 8 hours, promptly get the spheroid iron lithium phosphate of micron order particle diameter.
Embodiment 4
1) carries out a granulation: the hydrate that takes by weighing 1mol ferrous sulfate and iron protochloride; 1mol phosphoric acid (effective content by 85% volumetric concentration phosphoric acid calculates); Be dissolved in the deionized water of 3000ml; Add the 0.15mol complexing agent and gather third ethene, constantly stir, slowly add Quilonum Retard and the Lithium Sulphate hydrate soln 3000ml of 3mol;
2) above-mentioned solution is continued to stir time 1.5h in 120 ℃ of oil baths; Produce green precipitate, green precipitate is carried out suction filtration, washing obtains solid product;
3) with the gained solid product in vacuum drying oven in 70 ℃ of dry 8h; Dried presoma carries out ball mill pulverizing, and obtaining particle diameter is the presoma powder of 50nm;
4) be that 1: 0.06 ratio is dissolved in the deionized water with gained presoma powder and organic carbon Zusoplast 9002 according to mass ratio, after fully mixing, place vacuum drying oven, obtain subsequent use presoma in 70 ℃ of dry 20h;
5) carry out secondary granulation: subsequent use precursor powder of gained and macromolecule polymer solution are put in the enclosed vacuum container, utilized the stirrer high-speed stirring; Simultaneously; Spray the high molecular polymer Vilaterm and the Vestolen PP 7052 solution of subsequent use precursor powder weight 5% to the fog nozzle on vacuum vessel top, high molecular polymer Vilaterm and Vestolen PP 7052 strength of solution are 5% alcoholic solution, continue 2 hours; Be half-dried granular to material, particle diameter is at 50um;
The powder that 6) will pass through after the granulation carries out sintering, earlier in vacuum drying oven in 70 ℃ drying 6 hours, put into the inert atmosphere protection stove then, in 600 ℃ of sintering 8 hours, promptly get the spheroid iron lithium phosphate of micron order particle diameter.
Claims (7)
1. the preparation method of a high tap density nano-grade lithium iron phosphate is characterized in that, this high tap density nano-grade lithium iron phosphate is through the primary particle nanometer, and the preparation of the method for offspring micronization may further comprise the steps:
1) carry out a granulation: according to mol ratio is that 1: 1 ratio takes by weighing soluble ferrite and phosphoric acid is dissolved in the deionized water; According to the mol ratio of complexing agent and iron ion is that 0.1: 1 ratio adds complexing agent; And under constantly stirring, according to phosphonium ion: iron ion: the lithium ion mol ratio is that 1: 1: 1～3 ratio slowly adds lithium salt solution;
2) above-mentioned solution is continued to stir 1～2h in 110～140 ℃ of oil baths; To producing green precipitate, green precipitate is carried out suction filtration, washing obtains solid product;
3) with the gained solid product in vacuum drying oven in 60～80 ℃ of drying 6～10h; Dried presoma carries out ball mill pulverizing, and obtaining particle diameter is the presoma powder of 30～100nm;
4) be that 1: 0.03～0.1 ratio is dissolved in the deionized water with gained presoma powder and organic carbon according to mass ratio, after fully mixing, place vacuum drying oven, obtain subsequent use precursor powder in 60～80 ℃ of drying 12～24h;
5) carry out secondary granulation: subsequent use precursor powder of gained and macromolecule polymer solution are put in the enclosed vacuum container, utilized the stirrer high-speed stirring; Simultaneously, the fog nozzle that is positioned at vacuum vessel top sprays the macromolecule polymer solution of subsequent use precursor powder weight 1%～10%, continues 1-4h, is half-dried granular to material, and particle diameter is at 10um～100um;
The powder that 6) will pass through after the granulation carries out sintering, earlier in vacuum drying oven in 60～80 ℃ of drying 5～8h, put into the inert atmosphere protection stove then, in 550 ℃～700 ℃ sintering 6～10h, promptly get the spheroid iron lithium phosphate of micron order particle diameter.
2. the preparation method of high tap density nano-grade lithium iron phosphate according to claim 1 is characterized in that, described soluble ferrite is one or more in ferrous sulfate, iron protochloride or their hydrate.
3. the preparation method of high tap density nano-grade lithium iron phosphate according to claim 1 is characterized in that, the volumetric concentration of said phosphoric acid solution is 85%.
4. the preparation method of high tap density nano-grade lithium iron phosphate according to claim 1 is characterized in that, said complexing agent is one or more of terepthaloyl moietie, trolamine.
5. the preparation method of high tap density nano-grade lithium iron phosphate according to claim 1 is characterized in that, said lithium salt solution is one or more of Lithium Hydroxide MonoHydrate, Quilonum Retard, Lithium Sulphate or their hydrate.
6. the preparation method of high tap density nano-grade lithium iron phosphate according to claim 1 is characterized in that, said organic carbon is one or more of sucrose, glucose, Hydrocerol A, Zusoplast 9002.
7. the preparation method of high tap density nano-grade lithium iron phosphate according to claim 1; It is characterized in that; Described macromolecule polymer solution is one or more in Z 150PH, resol, glucose, sucrose, Vilaterm, the Vestolen PP 7052; Water-soluble or the pure solution that is configured to, strength of solution is 1%～10%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010293132XA CN101935028B (en) | 2010-09-27 | 2010-09-27 | Preparation method of nano lithium iron phosphate with high tap density |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010293132XA CN101935028B (en) | 2010-09-27 | 2010-09-27 | Preparation method of nano lithium iron phosphate with high tap density |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101935028A CN101935028A (en) | 2011-01-05 |
| CN101935028B true CN101935028B (en) | 2012-01-04 |
Family
ID=43388638
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201010293132XA Expired - Fee Related CN101935028B (en) | 2010-09-27 | 2010-09-27 | Preparation method of nano lithium iron phosphate with high tap density |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101935028B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102173403B (en) * | 2011-01-25 | 2013-08-21 | 山东省科学院能源研究所 | Preparation method of micro-nano lithium ferric phosphate (LiFePO4) positive electrode material of lithium-ion battery |
| CN102275890A (en) * | 2011-07-19 | 2011-12-14 | 彩虹集团公司 | Microwave-assisted synthesis method of nanometer lithium iron phosphate |
| CN104134782A (en) * | 2014-07-24 | 2014-11-05 | 安泰科技股份有限公司 | Anode material for nanometer LiFePO4 lithium ion battery and preparation method thereof |
| CN115893514A (en) * | 2022-10-12 | 2023-04-04 | 雅迪科技集团有限公司 | Sodium ion positive electrode material precursor, preparation method and application thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1305148C (en) * | 2005-01-12 | 2007-03-14 | 清华大学 | Method for preparing high-density spherical lithium iron phosphate and lithium iron manganese phosphate |
| CN100534898C (en) * | 2007-03-16 | 2009-09-02 | 北京工业大学 | Method for synthesizing lithium ion-cell anode material LiFePO4 |
| CN101279727A (en) * | 2008-05-20 | 2008-10-08 | 上海大学 | Low-temperature hydro-thermal synthesis for nano-lithium iron phosphate |
-
2010
- 2010-09-27 CN CN201010293132XA patent/CN101935028B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN101935028A (en) | 2011-01-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102201576B (en) | Porous carbon in situ composite lithium iron phosphate cathode material and preparation method thereof | |
| CN101428781B (en) | Conglobation type nanostructured lithium iron phosphate anode material and method for producing the same | |
| CN110474044A (en) | A kind of high-performance water system Zinc ion battery positive electrode and the preparation method and application thereof | |
| CN100448772C (en) | High density ultrafine composite ferric lithium phosphate anode material and preparation method | |
| CN104993121B (en) | A kind of nickel manganese blending anode material for lithium-ion batteries and preparation method thereof | |
| CN101944601B (en) | Method for uniformly coating carbon on nano lithium iron phosphate | |
| CN103956485B (en) | Lithium iron phosphate electrode material of a kind of three-dimensional hierarchical structure and preparation method thereof | |
| CN103972497B (en) | Lithium ion battery Co2snO4/ C nano composite negative pole material and preparation and application thereof | |
| CN101826617B (en) | Preparation method of lithium iron phosphate | |
| CN103579624B (en) | Modified lithium battery graphite crucible waste material negative material and preparation method thereof and application | |
| CN103594693B (en) | A kind of titanium dioxide/niobium-titanium oxide composite material and Synthesis and applications thereof | |
| CN101081696A (en) | Ferric phosphate lithium material for lithium ion powder cell and preparation method thereof | |
| CN102201275A (en) | Lithium salt and graphene composite material as well as preparation method and application thereof | |
| CN103066281A (en) | Synergistically modified lithium-iron-phosphate positive active material enveloped with graphene three-dimensional network and doped with metal ions and preparation method of lithium-iron-phosphate positive active material | |
| CN102881903A (en) | Preparation method of porous lithium iron phosphate powder | |
| CN102479945B (en) | The preparation method of spherical lithium iron phosphate anode material | |
| CN102275890A (en) | Microwave-assisted synthesis method of nanometer lithium iron phosphate | |
| CN103066255A (en) | A nano-metal coated sulfur composite material and applications thereof | |
| CN102842711A (en) | Zinc ferrite anode material of lithium ion battery and preparation method and application thereof | |
| CN105591100A (en) | Method of preparing lithium iron phosphate cathode material through hydrothermal method, and the cathode material | |
| CN105529439A (en) | Method for preparing lithium iron phosphate by hydrothermal method and lithium iron phosphate prepared by method | |
| CN109301194A (en) | Compound porous hard carbon material of phosphorus quantum dot and its preparation method and application | |
| CN104037412A (en) | Preparation method of multilevel-structured hollow nano-sphere of negative electrode material of high-performance lithium ion secondary battery | |
| CN101935028B (en) | Preparation method of nano lithium iron phosphate with high tap density | |
| CN106450186B (en) | A kind of preparation method, anode sizing agent and the application of lithium-ion battery anode material lithium manganese silicate/carbon composite |
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 | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20120104 Termination date: 20150927 |
|
| EXPY | Termination of patent right or utility model |