CN102903913B - The coated ferric phosphate of carbon, its carbon coated lithium ferrous phosphate composite material prepared and application thereof - Google Patents
The coated ferric phosphate of carbon, its carbon coated lithium ferrous phosphate composite material prepared and application thereof Download PDFInfo
- Publication number
- CN102903913B CN102903913B CN201210194270.1A CN201210194270A CN102903913B CN 102903913 B CN102903913 B CN 102903913B CN 201210194270 A CN201210194270 A CN 201210194270A CN 102903913 B CN102903913 B CN 102903913B
- Authority
- CN
- China
- Prior art keywords
- carbon
- coated
- ferric phosphate
- lithium
- phosphate
- 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
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
Abstract
The invention discloses the coated ferric phosphate of carbon, its carbon coated lithium ferrous phosphate composite material prepared and application thereof, the preparation method of the coated ferric phosphate of described carbon comprises the steps: that di-iron trioxide and phosphorus pentoxide are 1:(1 ~ 1.12 in Fe:P mol ratio by (1)) ratio mixing, fully grinding makes it to mix; (2) in step (1) gained mixed material, mix carbon source, then gained mixture is put into tube furnace, under inert gas protection; in 200 ~ 500 DEG C of pre-burnings 1 ~ 4 hour; again through 600 ~ 700 DEG C of high temperature sinterings 5 ~ 24 hours, be cooled to room temperature, levigately obtain the coated ferric phosphate of carbon.The present invention utilizes the coated ferric phosphate of described carbon to obtain carbon coated lithium ferrous phosphate composite material, its electric conductivity improves, chemical property especially heavy-current discharge performance significantly improves, and can be used as anode material for lithium-ion batteries, is widely used in the fields such as power-type lithium ion battery.
Description
(1) technical field
The present invention relates to the coated ferric phosphate of carbon, the carbon coated lithium ferrous phosphate composite material prepared by the coated ferric phosphate of this carbon and this composite material prepared by a kind of solid phase method application as anode material for lithium-ion batteries.
(2) background technology
Lithium ion battery is the novel green high-energy secondary battery occurred early 1990s, has become the emphasis that countries in the world are are competitively researched and developed.Positive electrode is an important component part of lithium ion battery, mainly contains the LiFePO 4 of lithium-containing transition metal (as cobalt, nickel and manganese etc.) oxide and olivine crystal structure at present.LiFePO 4, compared with other positive electrodes, has safer, more environmental protection, the more cheap and multiple advantage such as height ratio capacity.
At present, lithium ferrous phosphate as anode material of lithium ion battery is raw material mainly with ferric phosphate greatly, and Li source compound mixes, and adopts solid reaction process synthesis.Due in the high-temperature reaction process preparing LiFePO 4, the diffusion of ion is a slow process, therefore, the activity of ferric phosphate is to reaction important, there is larger difference because of its structure transitivity aspect in the ferric phosphate prepared of distinct methods, prepared LiFePO 4 performance inconsistency is also larger.Traditional industry is produced the method mainly wet chemistry method of ferric phosphate.One obtains by directly reacting with phosphoric acid and trivalent iron salt, and another kind of method adds phosphoric acid in the presence of an oxidizer with ferrous salt to make.Use the ferric phosphate that existing method is produced, tap density is low, particle size distribution is wide, agglomeration is relatively serious, be difficult to obtain ferrousphosphate lithium material of good performance.
(3) summary of the invention
The present invention's first object is to provide a kind of coated ferric phosphate of carbon with high reaction activity, and the preparation method of the coated ferric phosphate of this carbon is simple to operate, with low cost, without waste water, be easy to realize industrialization.
The present invention's second object is to provide a kind of carbon coated lithium ferrous phosphate composite material obtained by the coated ferric phosphate of carbon, and this conductivity of composite material can improve, and chemical property especially heavy-current discharge performance significantly improves.
The present invention's the 3rd object is that described carbon coated lithium ferrous phosphate composite material is applied to anode material for lithium-ion batteries.
Illustrate technical scheme of the present invention below.
The invention provides the coated ferric phosphate of a kind of carbon, in the coated ferric phosphate of described carbon, carbon content is 1 ~ 20wt%, and be preferably 1 ~ 10wt%, its preparation method comprises the steps:
(1) be 1:(1 ~ 1.12 by di-iron trioxide and phosphorus pentoxide in Fe:P mol ratio) ratio mixing, fully grinding makes it to mix;
(2) in step (1) gained mixed material, mix carbon source, then gained mixture is put into tube furnace, under inert gas protection; in 200 ~ 500 DEG C of pre-burnings 1 ~ 4 hour; again through 600 ~ 700 DEG C of high temperature sinterings 5 ~ 24 hours, be cooled to room temperature, levigately obtain the coated ferric phosphate of carbon.
In described step (1), can adopt conventional method that di-iron trioxide and phosphorus pentoxide are mixed, such as ground and mixed 2 ~ 20 hours on ball mill.Usually, for making mixture reach well-mixed effect, can add suitable alcohols before the milling, the volume that adds of alcohol is generally 20 ~ 200mL/mol with the molar basis of di-iron trioxide.
In described step (2), described carbon source is preferably polyethylene or polypropylene or pitch, and carbon source can feed intake with reference to the carbon content in the coated ferric phosphate of the carbon of actual needs.Described inert gas be not with the air-flow of reaction system effect, preferred nitrogen air-flow or argon gas stream.The flow velocity of described inert gas is recommended as 5 ~ 30 liters/min.
In described step (2), preferred described mixture first with ramp to 200 ~ 500 of 5 ~ 10 DEG C/min DEG C pre-burning 1 ~ 4 hour, then with ramp to 600 ~ 700 of 5 ~ 10 DEG C/min DEG C high temperature sintering 5 ~ 24 hours.
The present invention specifically recommends the preparation method of the coated ferric phosphate of described carbon to carry out in accordance with the following steps:
(1) be 1:(1 ~ 1.12 by di-iron trioxide and phosphorus pentoxide in Fe:P mol ratio) ratio mixing, and add alcohol, alcohol add volume with the molar basis of di-iron trioxide for 20 ~ 200mL/mol, then on ball mill mix 5 ~ 20 hours, make it to mix;
(2) in step (1) gained mixed material, mix polyethylene or polypropylene or pitch; then gained mixture is put into tube furnace; under nitrogen or argon gas stream protection; first with ramp to 200 ~ 500 of 5 ~ 10 DEG C/min DEG C pre-burning 1 ~ 4 hour; again with ramp to 600 ~ 700 of 5 ~ 10 DEG C/min DEG C high temperature sintering 5 ~ 24 hours; be cooled to room temperature, levigately obtain the coated ferric phosphate of carbon.
The coated ferric phosphate of carbon prepared by the present invention is not containing the crystallization water, and average grain diameter is 1 ~ 5 micron, and tap density is greater than 1.2g/cm
3, reactivity is high.
Present invention also offers the carbon coated lithium ferrous phosphate composite material prepared by the coated ferric phosphate of described carbon, concrete preparation method is: be (0.95 ~ 1.05) by coated to lithium compound and carbon ferric phosphate according to the mol ratio of Li:Fe: the ratio of 1 mixes, under reducing atmosphere, sinter 4 ~ 30 hours in 600 ~ 800 DEG C, cooling is levigate afterwards obtains carbon coated lithium ferrous phosphate composite material.Described lithium compound is the compound containing lithium source, as lithium hydroxide, lithium carbonate, lithium nitrate etc.Lithium compound and the coated ferric phosphate of carbon mix by the mode of ball milling, and Ball-milling Time is recommended as 5 ~ 20 hours.The N of described reducing atmosphere to be volume ratio be 5 ~ 9:1
2with H
2mixed atmosphere or volume ratio be Ar and the H of 5 ~ 9:1
2mixed atmosphere.The flow velocity of described reproducibility air-flow is recommended as 5 ~ 30 liters/min.
Carbon coated lithium ferrous phosphate composite material electric conductivity of the present invention improves, and chemical property especially heavy-current discharge performance significantly improves, and can be used as anode material for lithium-ion batteries, is widely used in the fields such as power-type lithium ion battery.
Compared with prior art, its beneficial effect is mainly reflected in the present invention:
(1) the present invention adopts a step solid phase method to prepare the coated iron phosphate material of carbon, the raw material sources adopted extensively, be easy to get, cheap, preparation method is simple, discharges without waste water and gas, thus environmentally friendly; The carbon coated ferric phosphate reactivity of preparation is high.
(2) carbon cladded ferrous lithium phosphate/carbon composite electric conductivity that the present invention makes for raw material with the coated ferric phosphate of carbon improves, chemical property especially heavy-current discharge performance significantly improves, can be used as anode material for lithium-ion batteries, be widely used in the fields such as power-type lithium ion battery.
(4) accompanying drawing explanation
Fig. 1 is the XRD diffracting spectrum of the coated ferric phosphate of carbon that embodiment 1 obtains.
Fig. 2 is the XRD diffracting spectrum of the carbon coated lithium ferrous phosphate composite material that embodiment 1 obtains.
Fig. 3 is the first charge-discharge curve of lithium ion battery in different multiplying of embodiment 1 making.
(5) specific implementation method
Below in conjunction with specific embodiment, the present invention is described further, but protection scope of the present invention is not limited in this:
Embodiment 1
0.5 mole of di-iron trioxide and 0.5 mole of phosphorus pentoxide are mixed, put into nylon tank, and add the alcohol of 80 milliliters, after ball mill mixes 2 hours, put into tube furnace carry out thermal response by mixing 15 grams of polypropylene (Mw is at about 10W ~ 60W) in this mixture, under the blanket of nitrogen of 5 liters/min, rise to 400 DEG C of pre-burnings 2 hours with the speed of 5 DEG C/min, rise to 700 DEG C of high temperature sinterings 8 hours with identical heating rate again, be then cooled to room temperature.Recording carbon percentage by weight in gained composite material is 2.5%, reference standard card, and be the ferric phosphate (XRD diffracting spectrum is shown in Fig. 1) that crystal formation is intact, products therefrom particle diameter is 1 ~ 2 micron, and tap density is 1.35g/cm
3.
0.98 mole of LiOH is joined in the coated ferric phosphate of carbon, ball milling 10 hours, put into stove at logical N
2with H
2be warming up to 650 DEG C of insulations 10 hours under the condition of the mixed atmosphere of (volume ratio 9:1), the flow velocity of mixed atmosphere is 10 liters/min, again levigately obtains carbon coated lithium ferrous phosphate composite material (XRD diffracting spectrum is shown in Fig. 2) after naturally cooling.
Electrode is made as follows with obtained carbon cladded ferrous lithium phosphate.
Take carbon cladded ferrous lithium phosphate respectively with the mass ratio of 80:10:10: acetylene black: polytetrafluoroethylene, make electrode after grinding evenly, metal lithium sheet is negative pole, and electrolyte is 1mol/L LiPF
6/ EC – DMC (1:1), polypropylene microporous film is barrier film, is assembled into simulation lithium ion battery.Fig. 3 is the first charge-discharge curve of respective battery in different multiplying, and the discharge capacity of 5C is 112mAh/g, and electrochemical charge transfger impedance is 90 Ω.
Embodiment 2
0.5 mole of di-iron trioxide and 0.56 mole of phosphorus pentoxide are mixed, put into nylon tank, and add the alcohol of 100 milliliters, after ball mill mixes 4 hours, put into tube furnace carry out thermal response by mixing 20 grams of polypropylene (Mw is at about 10W ~ 60W) in this mixture, under the blanket of nitrogen of 10 liters/min, rise to 300 DEG C of pre-burnings 4 hours with the speed of 10 DEG C/min, rise to 700 DEG C of high temperature sinterings 16 hours with identical heating rate again, be then cooled to room temperature.Recording carbon percentage by weight in gained composite material is 4.6%, reference standard card, is the ferric phosphate that crystal formation is intact, and products therefrom particle diameter is 3 – 5 microns, and tap density is 1.24/cm
3.
By 0.51 mole of Li
2cO
3join in the coated ferric phosphate of carbon, ball milling 10 hours, put into stove at logical N
2with H
2be warming up to 600 DEG C of insulations 20 hours under the condition of the mixed atmosphere of (volume ratio 8:1), the flow velocity of mixed atmosphere is 10 liters/min, again levigately obtains carbon coated lithium ferrous phosphate composite material after naturally cooling.
Obtained carbon cladded ferrous lithium phosphate makes electrode by the method for embodiment 1, and be assembled into simulation lithium ion battery, the discharge capacity of its 5C is close to 120mAh/g, and electrochemical charge transfger impedance is 100 Ω.
Embodiment 3
0.5 mole of di-iron trioxide and 0.52 mole of phosphorus pentoxide are mixed, put into nylon tank, and add the alcohol of 80 milliliters, after ball mill mixes 4 hours, put into tube furnace carry out thermal response by mixing 25 grams of polyethylene (Mw is at about 80W ~ 500W) in this mixture, under the blanket of nitrogen of 5 liters/min, rise to 400 DEG C of pre-burnings 1 hour with the speed of 5 DEG C/min, rise to 600 DEG C of high temperature sinterings 24 hours with identical heating rate again, be then cooled to room temperature.Recording carbon percentage by weight in gained composite material is 3.2%, reference standard card, is the ferric phosphate that crystal formation is intact, and products therefrom particle diameter is 2 – 5 microns, and tap density is 1.31/cm
3.
By 1.02 moles of LiNO
3join in the coated ferric phosphate of carbon, ball milling 12 hours, put into stove at logical Ar and H
2be warming up to 700 DEG C of insulations 10 hours under the condition of the mixed atmosphere of (volume ratio 9:1), the flow velocity of mixed atmosphere is 12 liters/min, again levigately obtains carbon coated lithium ferrous phosphate composite material after naturally cooling.
Obtained carbon cladded ferrous lithium phosphate makes electrode by the method for embodiment 1, and be assembled into simulation lithium ion battery, the discharge capacity of its 5C is close to 115mAh/g, and electrochemical charge transfger impedance is 103 Ω.
Embodiment 4
0.5 mole of di-iron trioxide and 0.54 mole of phosphorus pentoxide are mixed, put into nylon tank, and add the alcohol of 100 milliliters, after ball mill mixes 4 hours, put into tube furnace carry out thermal response by mixing 25 grams of pitches in this mixture, under the blanket of nitrogen of 10 liters/min, rise to 300 DEG C of pre-burnings 4 hours with the speed of 5 DEG C/min, rise to 700 DEG C of high temperature sinterings 8 hours with identical heating rate again, be then cooled to room temperature.Recording carbon percentage by weight in gained composite material is 3.8%, reference standard card, is the ferric phosphate that crystal formation is intact, and products therefrom particle diameter is 2 – 4 microns, and tap density is 1.28/cm
3.
0.98 mole of LiOH is joined in the coated ferric phosphate of carbon, ball milling 10 hours, put into stove at logical Ar and H
2be warming up to 650 DEG C of insulations 20 hours under the condition of the mixed atmosphere of (volume ratio 7:1), the flow velocity of mixed atmosphere is 10 liters/min, again levigately obtains carbon coated lithium ferrous phosphate composite material after naturally cooling.
Obtained carbon cladded ferrous lithium phosphate makes electrode by the method for embodiment 1, and be assembled into simulation lithium ion battery, the discharge capacity of its 5C is close to 121mAh/g, and electrochemical charge transfger impedance is 98 Ω.
Claims (10)
1. the coated ferric phosphate of carbon, is characterized in that: in the coated ferric phosphate of described carbon, carbon content is 1 ~ 20wt%, and its preparation method comprises the steps:
(1) be 1:(1 ~ 1.12 by di-iron trioxide and phosphorus pentoxide in Fe:P mol ratio) ratio mixing, fully grinding makes it to mix;
(2) in step (1) gained mixed material, carbon source is mixed; then gained mixture is put into tube furnace; under inert gas protection; in 200 ~ 500 DEG C of pre-burnings 1 ~ 4 hour; again through 600 ~ 700 DEG C of high temperature sinterings 5 ~ 24 hours; be cooled to room temperature, levigately obtain the coated ferric phosphate of carbon.
2. the coated ferric phosphate of carbon as claimed in claim 1, is characterized in that: described is fully ground to: on ball mill, mix 2 ~ 20 hours.
3. the coated ferric phosphate of carbon as claimed in claim 1 or 2, it is characterized in that: in described step (1), before the milling, in di-iron trioxide and phosphorus pentoxide, add alcohol, described alcohol add volume with the molar basis of di-iron trioxide for 20 ~ 200mL/mol.
4. the coated ferric phosphate of carbon as claimed in claim 1, is characterized in that: described carbon source is polyethylene or polypropylene or pitch.
5. the coated ferric phosphate of carbon as claimed in claim 1, is characterized in that: described inert gas is nitrogen stream or argon gas stream.
6. the coated ferric phosphate of carbon as claimed in claim 1, it is characterized in that: in described step (2), mixture first with ramp to 200 ~ 500 of 5 ~ 10 DEG C/min DEG C pre-burning 1 ~ 4 hour, then with ramp to 600 ~ 700 of 5 ~ 10 DEG C/min DEG C high temperature sintering 5 ~ 24 hours.
7. the coated ferric phosphate of carbon as claimed in claim 1, is characterized in that: described method is carried out in accordance with the following steps:
(1) be 1:(1 ~ 1.12 by di-iron trioxide and phosphorus pentoxide in Fe:P mol ratio) ratio mixing, and add alcohol, alcohol add volume with the molar basis of di-iron trioxide for 20 ~ 200mL/mol, then mixing 5 ~ 20 hours on ball mill, make it to mix;
(2) in step (1) gained mixed material, mix polyethylene or polypropylene or pitch; then gained mixture is put into tube furnace; under nitrogen or argon gas stream protection; first with ramp to 200 ~ 500 of 5 ~ 10 DEG C/min DEG C pre-burning 1 ~ 4 hour; again with ramp to 600 ~ 700 of 5 ~ 10 DEG C/min DEG C high temperature sintering 5 ~ 24 hours; be cooled to room temperature, levigately obtain the coated ferric phosphate of carbon.
8. the carbon coated lithium ferrous phosphate composite material prepared by the coated ferric phosphate of carbon according to claim 1, described composite material is prepared especially by following method: be (0.95 ~ 1.05) by coated to lithium compound and carbon ferric phosphate according to the mol ratio of Li:Fe: the ratio of 1 mixes, under reducing atmosphere, sinter 4 ~ 30 hours in 600 ~ 800 DEG C, cooling is levigate afterwards obtains carbon coated lithium ferrous phosphate composite material; Described lithium compound is lithium hydroxide, lithium carbonate or lithium nitrate.
9. carbon coated lithium ferrous phosphate composite material as claimed in claim 8, is characterized in that: the N of described reducing atmosphere to be volume ratio be 5 ~ 9:1
2with H
2mixed atmosphere or volume ratio be Ar and the H of 5 ~ 9:1
2mixed atmosphere.
10. carbon coated lithium ferrous phosphate composite material as claimed in claim 8 is as the application of anode material for lithium-ion batteries.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201210194270.1A CN102903913B (en) | 2012-06-13 | 2012-06-13 | The coated ferric phosphate of carbon, its carbon coated lithium ferrous phosphate composite material prepared and application thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201210194270.1A CN102903913B (en) | 2012-06-13 | 2012-06-13 | The coated ferric phosphate of carbon, its carbon coated lithium ferrous phosphate composite material prepared and application thereof |
Publications (2)
Publication Number | Publication Date |
---|---|
CN102903913A CN102903913A (en) | 2013-01-30 |
CN102903913B true CN102903913B (en) | 2015-10-28 |
Family
ID=47576053
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201210194270.1A Expired - Fee Related CN102903913B (en) | 2012-06-13 | 2012-06-13 | The coated ferric phosphate of carbon, its carbon coated lithium ferrous phosphate composite material prepared and application thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN102903913B (en) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110970605A (en) * | 2018-09-30 | 2020-04-07 | 深圳市贝特瑞纳米科技有限公司 | Carbon-coated ferrous phosphate, preparation method, carbon-coated lithium iron phosphate prepared by using carbon-coated ferrous phosphate and application |
CN112397698B (en) * | 2020-11-16 | 2022-02-18 | 合肥国轩高科动力能源有限公司 | Composite conductive agent coated lithium iron phosphate material and preparation method and application thereof |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101659406A (en) * | 2009-09-25 | 2010-03-03 | 四川大学 | Method for preparing iron phosphate from ferrophosphorus |
CN102201576A (en) * | 2011-04-25 | 2011-09-28 | 北京科技大学 | Porous carbon in situ composite lithium iron phosphate cathode material and preparation method thereof |
-
2012
- 2012-06-13 CN CN201210194270.1A patent/CN102903913B/en not_active Expired - Fee Related
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101659406A (en) * | 2009-09-25 | 2010-03-03 | 四川大学 | Method for preparing iron phosphate from ferrophosphorus |
CN102201576A (en) * | 2011-04-25 | 2011-09-28 | 北京科技大学 | Porous carbon in situ composite lithium iron phosphate cathode material and preparation method thereof |
Also Published As
Publication number | Publication date |
---|---|
CN102903913A (en) | 2013-01-30 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN100461507C (en) | Making method for nano LiFePO4-carbon composite cathode material | |
CN101740752B (en) | Core-shell composite anode material for lithium ion battery and preparation method thereof | |
CN102364726B (en) | Method for producing iron lithium manganese phosphate composite positive electrode material used in lithium ion battery through carbon reduction | |
CN103078105B (en) | Lithium ion battery, positive active material thereof and preparation method of positive active material | |
CN102623708A (en) | Preparation method of lithium vanadium phosphate (Li3V2(PO4)3)/graphene composite material for positive electrode of lithium ion battery | |
CN101582498A (en) | Method for preparing nanometer ferrous phosphate lithium /carbon composite material | |
CN101752562B (en) | Compound doped modified lithium ion battery anode material and preparation method thereof | |
JP2024516049A (en) | Manufacturing method of lithium manganese iron phosphate, positive electrode material and lithium ion battery | |
CN103515594A (en) | Carbon coated lithium manganese phosphate/lithium iron phosphate core-shell structure material as well as preparation method thereof | |
CN105185954A (en) | LiAlO2 coated LiNi1-xCoxO2 lithium-ion battery positive electrode material and preparation method thereof | |
CN102386412A (en) | Lithium ion battery anode Li3V2(PO4)3/C composite material and preparation method thereof | |
CN102148367A (en) | Method for preparing lithium-ion battery anode material of lithium iron phosphate | |
CN103000898A (en) | Preparation method for carbon compounded lithium ferromanganese phosphate used for lithium ion battery | |
CN102832381A (en) | Preparation method of high-voltage cathode material Lil+xMn3/2-yNil/2-zMy+zO4 of lithium ion battery with long service life | |
CN101651198B (en) | Doping lithium iron phosphate material and preparation method and application thereof | |
CN103779563A (en) | Method for preparing copper/carbon-coated lithium iron phosphate | |
CN114094060A (en) | Preparation method of high-voltage positive electrode material with core-shell structure | |
CN102593449B (en) | Lithium iron phosphate material simultaneously doped with metal ions and fluoride ions and synthetic method thereof | |
CN107026268B (en) | A kind of preparation method of anode material for lithium-ion batteries iron molybdate lithium | |
CN100527482C (en) | Making method for LiFePO4-carbon composite cathode material of lithium ion battery | |
CN102903913B (en) | The coated ferric phosphate of carbon, its carbon coated lithium ferrous phosphate composite material prepared and application thereof | |
CN100418252C (en) | Preperative method for ferrous phosphate radical lithium salt of lithium ion secondary cell active material | |
CN102983333A (en) | Novel preparation method of lithium vanadium phosphate/carbon composite material for positive pole of lithium ion battery | |
CN103390751A (en) | Method of preparing lithium battery vanadate positive materials by utilizing hydrothermal method | |
CN107834054B (en) | Preparation method of lithium nickel manganese oxide-graphene composite material for lithium ion battery |
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 | ||
CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20151028 Termination date: 20200613 |