CN102225753B - Preparation method for lithium ion battery cathode materials - Google Patents

Preparation method for lithium ion battery cathode materials Download PDF

Info

Publication number
CN102225753B
CN102225753B CN2011101231156A CN201110123115A CN102225753B CN 102225753 B CN102225753 B CN 102225753B CN 2011101231156 A CN2011101231156 A CN 2011101231156A CN 201110123115 A CN201110123115 A CN 201110123115A CN 102225753 B CN102225753 B CN 102225753B
Authority
CN
China
Prior art keywords
calcining
time
temperature
lithium
presoma
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.)
Active
Application number
CN2011101231156A
Other languages
Chinese (zh)
Other versions
CN102225753A (en
Inventor
高明霞
潘洪革
叶欣
刘永锋
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Zhejiang University ZJU
Original Assignee
Zhejiang University ZJU
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Zhejiang University ZJU filed Critical Zhejiang University ZJU
Priority to CN2011101231156A priority Critical patent/CN102225753B/en
Publication of CN102225753A publication Critical patent/CN102225753A/en
Application granted granted Critical
Publication of CN102225753B publication Critical patent/CN102225753B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

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

Abstract

The invention provides a preparation method for lithium ion battery cathode materials. Specifically, various synthesis methods like solid phase method and liquid phase method are adopted to prepare a precursor of lithium ion battery cathode materials such as LiFePO4. Then the precursor is subjected to joint calcination at a changing temperature. Thus, optimal design and control of the structure and appearance of the synthesized lithium ion battery cathode materials can be realized. Therefore, a preparation method for lithium ion battery electrode materials with high-rate and ultra high-rate charge-discharge performance is obtained.

Description

A kind of preparation method of anode material for lithium-ion batteries
Technical field
The present invention relates to the preparation method of anode material for lithium-ion batteries, belong to the energy and material technical field, be specifically related to a kind ofly carry out alternating temperature by the presoma to the anode material for lithium-ion batteries that adopts the various synthetic methods preparations such as solid phase method, liquid phase method and unite calcining, reach optimal design and control to synthesis of anode material of lithium-ion battery structure and pattern, thereby acquisition has the preparation method of the lithium ion battery electrode material of high magnification and ultra-high magnifications charge-discharge characteristic.
Background technology
Lithium ion battery is the green secondary cell that grows up the nineties in 20th century, compare with secondary cells such as traditional plumbic acid, NI-G, ni-mhs, advantages such as lithium ion battery is high with its reversible capacity, good cycling stability, energy density are high, memory-less effect and enjoy favor are used widely on the small-sized movable power supply.Traditional anode material for lithium-ion batteries is mainly cobalt acid lithium (LiCoO 2), owing to containing noble metal, its price is more expensive, substantially account for the over half of lithium battery cost, and its limited capacity has also restricted lithium ion battery as the requirement with high-energy-density, long circulation life, green non-pollution and low-cost secondary power supply such as electric tool, electric motor car and hybrid electric vehicle.Thereby the Development of New Generation high-performance, green anode material for lithium-ion batteries is significant cheaply.
LiFePO4 (LiFePO 4) anode material for lithium-ion batteries has extended cycle life owing to having, security performance is good, raw material sources are abundant, cost is low, avirulence and the electric automobile etc. that advantage is considered to application prospect most such as fail safe is good be with one of dynamic lithium battery positive electrode, and obtained tentative application.But LiFePO 4The shortcoming that material electronics conductivity and ionic conductivity are low has restricted its charge-discharge performance under high magnification, thereby has hindered its scale on anode material for lithium-ion batteries to use.Common modified method mainly contains LiFePO at present 4The nanometer of material and porous, material with carbon-coated surface and doping etc.
Up to the present, usually carry out one-step calcination by the presoma to lithium ion anode material in the prior art and obtain positive electrode.This one-step calcination method is owing to being difficult to control simultaneously the structure factor that in synthetic material, the material high rate capability is played a crucial role, comprise high conductivity content mutually etc. in crystallinity, particle size and material, thereby the high rate capability of synthetic positive electrode can not get effective assurance.
Therefore, need the new technological measure of exploitation, realize the design of anode material for lithium-ion batteries structural optimization and control, make this material have good crystallinity, particle size is less and the high conductivity compound is appropriate advantage concurrently.
Summary of the invention
The invention provides a kind of method for preparing anode material for lithium-ion batteries, the method is united calcining by the presoma to the synthesis of anode material of lithium-ion battery that adopts solid phase method or Liquid preparation methods carries out step calcination under the different temperatures section alternating temperature, optimal design and the control of realization to synthetic this material structure and performance, have raising lithium ion anode material crystallinity concurrently, control its particle size, thereby obtain to have the anode material for lithium-ion batteries of high magnification and ultra-high magnifications charge-discharge characteristic.
Particularly, the preparation method of anode material for lithium-ion batteries provided by the invention comprises the following steps:
(1) provide the presoma of anode material for lithium-ion batteries;
(2) this presoma is carried out alternating temperature and unite calcining;
Wherein, described alternating temperature is united calcining and is comprised this presoma is implemented at least twice calcining in the temperature range of 300-900 ℃.
In one embodiment, the anode material for lithium-ion batteries for preparing by the inventive method is LiFePO 4Cell positive material.Uniting calcining by alternating temperature of the present invention has realized this LiFePO 4The optimal design of material structure and performance and control have also improved LiFePO 4The crystallinity of lithium ion anode material, control its particle size, original position is introduced the Fe of high conductivity simultaneously 2P and FeP.
Description of drawings
Fig. 1 is the resulting LiFePO of embodiment 1 4The stereoscan photograph of material.
Fig. 2 is the resulting LiFePO of embodiment 1 4The X-ray diffracting spectrum of material.
Fig. 3 is the resulting LiFePO of embodiment 1 4Discharge capacity under different multiplying.
Fig. 4 is for adopting the identical presoma of embodiment 1, and under identical atmosphere, respectively through (a) 600 ℃ of calcinings 20 hours, (b) 700 ℃ of calcinings are 4 hours, (c) 700 ℃ of calcinings 10 hours and (d) 800 ℃ of LiFePO that calcining obtained in 2 hours 4The SEM pattern of material.
Fig. 5 is for adopting the identical presoma of example 1, and under identical calcination atmosphere, respectively through (a) 600 ℃ of calcinings 20 hours, (b) 700 ℃ of calcinings are 4 hours, (c) 700 ℃ of calcinings 10 hours and (d) 800 ℃ of LiFePO that calcining obtained in 2 hours 4The discharge capacity of material under different discharge-rates.
Embodiment
The preparation method of anode material for lithium-ion batteries provided by the invention comprises that (1) provides the presoma of anode material for lithium-ion batteries; (2) this presoma is carried out alternating temperature and unite calcining, wherein, described alternating temperature is united calcining and is comprised this presoma is implemented at least twice calcination process in the temperature range of 300-900 ℃.
In preparation method of the present invention, the lithium ion anode material presoma the technology that can adopt any preparation lithium ion anode material presoma used in the art is provided.These technology include but not limited to: the various raw material source (such as source of iron, phosphorus source, lithium source and optional carbon source etc.) that will synthesize presoma in solid phase method is directly carried out the mechanical ball break-in and is become presoma under solid phase; Raw material are carried out the method for ball milling and process synthetic presoma through desolventizing in the liquid phase mediums such as distilled water, ethanol, acetone; The presoma that in liquid phase method, the methods such as sol-gel process, spray drying process, coprecipitation obtain, etc.
After the precursor of lithium ionic cell positive material oven dry that will obtain by above-mentioned any method, grinding, then unite calcining by alternating temperature, thereby form positive electrode.Implement alternating temperature and unite when calcining, directly under reducing atmosphere or inert atmosphere, carry out the substep alternating temperature of different time to making presoma and unite calcining in the temperature range of 300-900 ℃.
In a preferred embodiment, the substep alternating temperature of the present invention calcining step of uniting in calcining can carry out at twice.The temperature of calcining can be less than calcining heat for the second time for the first time, but the temperature of calcining also can be greater than calcining heat for the second time for the first time.
In one embodiment, alternating temperature of the present invention is united calcining and is comprised calcination process twice: at first at temperature lower calcination 0.5-25 hour of 300-750 ℃, calcined 0.5-15 hour under 600-900 ℃ more subsequently.
For example, can be at first 300～750 ℃, preferred 400～700 ℃, more preferably calcine for the first time in the shorter time period at the temperature of 500～650 ℃, for example calcination time is 0.5～25 hour, preferred 5～20 hours, more preferably 10～20 hours; Subsequently again 600-900 ℃, preferred 600～800 ℃, more preferably calcine for the second time under 650～750 ℃, calcination time is 1～20 hour, preferred 1～15 hour, more preferably 1～6 hour.Also can be first 600-900 ℃, preferred 600～800 ℃, more preferably calcine for the first time under 650～750 ℃, subsequently again 300～750 ℃, preferred 400～700 ℃, more preferably calcine for the second time at the temperature of 500～650 ℃.
In a preferred embodiment, for the first time 400～700 ℃ of calcinings 5～20 hours, then for the second time 600～800 ℃ of calcinings 1～15 hour.
In another preferred embodiment, for the first time 600～800 ℃ of calcinings 1～15 hour, then for the second time 400～700 ℃ of calcinings 5～20 hours.
In a preferred embodiment, for the first time 500～650 ℃ of calcinings 10～20 hours, then for the second time 650～750 ℃ of calcinings 1～6 hour.
In another preferred embodiment, for the first time 650～750 ℃ of calcinings 1～6 hour, then for the second time 500～650 ℃ of calcinings 10～20 hours.
Before the enforcement alternating temperature is united calcining, can also carry out presintering the temperature of 250～400 ℃ in inert atmosphere to the presoma that makes.Presintering is conducive to improve the final performance of material to a certain extent, and presintering is 1～10 hour usually.
The alternating temperature that carries out implementing after presintering is united calcining and can under reducing atmosphere or inert atmosphere, in the temperature range of 500-900 ℃, be carried out the substep alternating temperature of different time and unite calcining.
Can there is no the interval between each calcining step of step calcination, for example directly variations in temperature is arrived next step, but exist the interval there is no adverse influence between each step calcining yet.For example, can after first step calcining, material cooled be arrived room temperature, the second step calcining is carried out at the interval again after any long a period of time, as long as in interval procedure, deliquescence does not occur, this can realize by for example being placed in drier.
Calcination atmosphere can be the inert gases such as nitrogen or argon gas, can be also reducing atmosphere, as contains the mists such as the argon hydrogen of a small amount of hydrogen or nitrogen hydrogen.
In the methods of the invention, the source of iron that obtains presoma can be ferrous oxalate, ferric nitrate, ironic citrate, ferric phosphate etc., the phosphorus source can be ammonium dihydrogen phosphate, ferric phosphate etc., the lithium source can be lithium carbonate, lithium citrate, lithium hydroxide, lithium phosphate etc., and carbon source can be carbohydrate and the polymer such as polyvinyl alcohol (PVA) and polytetrafluoroethylene such as the acids such as alcohols, citric acid and laurate, sucrose and glucose such as ethylene glycol.
The inventor finds, at preparation LiFePO 4During anode material for lithium-ion batteries, if calcining for the first time generally need to enter calcining for the second time (being " high-temperature calcination " this moment) again for low temperature calcination (for example lower than 650 ℃ or lower than the temperature of calcining for the second time) after obtaining good crystallinity.If but calcining for the first time generally needs to generate a small amount of Fe for high-temperature calcination (for example higher than 650 ℃ or lower than the temperature of calcining for the second time) 2After P/FeP, then enter second step calcining (being low temperature calcination this moment).
In one embodiment, prepare LiFePO by the inventive method 4Anode material for lithium-ion batteries, the LiFePO that finally obtains 4The Fe that contains 1～15 % by weight in during anode material for lithium-ion batteries 2P/FeP.And Fe 2The content of P/FeP can be by alternating temperature being united calcining calcining heat and calcination time regulate and change.
The inventor also finds, when calcining was for low temperature calcination for the first time, the crystallinity of calcining can improve and improve by high-temperature calcination (calcining for the second time) process subsequently for the first time.When calcining as high-temperature calcination for the first time, even the synthetic Fe of calcining for the first time 2P/FeP, this high-temperature calcination may also can produce Fe to calcining for the second time (low temperature calcination) process 2P/FeP is favourable.
The LiFePO for preparing by the present invention 4The primary particle of material is of a size of nearly hundred nanometers to the hundreds of nanometer, mainly at 100nm～500nm.When there was reunion in primary particle, the size of agglomerated particle preferably was no more than 2 μ m.Because particle size is not several excessive tiny nanoscale degree to tens nanometers, thereby when the preparation electrode, the electrode preparation manipulation is easier to respect to several materials to tens nanometers, and is conducive to the higher compacted density of electrode acquisition.In addition, the LiFePO for preparing by the present invention 4Material granule also has good dispersiveness, with the LiFePO of existing method (as the one-step calcination method) acquisition in this area 4Material granule is compared, and the reunion degree of particle is less.
When using carbon source to prepare presoma, the LiFePO that preferably prepares by the inventive method 4The particle surface of material can realize that carbon coats by carbon source, thereby improves the surface conductivity of material, also plays the effect of controlling particle size simultaneously, can effectively improve LiFePO 4The dynamic performance of material and high rate performance.
When not using carbon source to prepare presoma, the LiFePO of the present invention's preparation 4Material can be substantially carbon-free LiFePO 4Material, its high magnification and ultra-high magnifications performance can be by the Fe of material situ generation 2P and FeP guarantee, for example original position generates the Fe of 1-15 % by weight, preferred 3.5～10 % by weight 2P and FeP.In addition, the LiFePO that does not have carbon coated 4Material has higher tap density, is conducive to LiFePO 4The raising of electrode volume capacity density.
Method applicability of the present invention is wide, need not introduce extras or reforming equipment, and calcine technology parameter adjustable extent is wide, can reach effective control and adjusting to structure and the particle size of anode material for lithium-ion batteries.Especially as synthetic LiFePO 4Material can obtain excellent high magnification and ultra-high magnifications charge-discharge performance as anode material for lithium-ion batteries,
Embodiment
The present invention may be better understood for following examples, but the present invention is not limited to following examples.
Embodiment 1
Take mol ratio as the ferrous oxalate of 1: 1: 1, ammonium dihydrogen phosphate, lithium hydroxide be as raw material, employing and metal cation mol ratio are that the ethylene glycol of 1: 1 is carbon source, above-mentioned original material is carried out the mechanical ball mill in ethanol medium on ball mill, Ball-milling Time is 4 hours.The ball milling product is stirred desolventizing and further dry in drying box under 80 ℃, after drying, powder body material carries out ball mill grinding again, and then in containing the argon hydrogen mixed atmosphere of a small amount of hydrogen, calcining is 20 hours under 600 ℃, then calcined again under 700 ℃ 4 hours, obtain containing a small amount of Fe 2The carbon of P coats LiFePO 4Material.Electro-chemical test shows, the capacity of resulting materials under 5C, 10C and 20C discharge-rate reaches and reach respectively 120,110 and 100mAh/g.
To the resulting LiFePO of embodiment 1 4Material scans with ESEM, and the photo that obtains is shown in Fig. 1.Demonstrate synthetic LiFePO in figure 4Has the more tiny particle size that is evenly distributed.The primary particle size is substantially below 500nm, and favorable dispersibility.The particle size of tiny dispersion is conducive to LiFePO 4Material obtains good high rate performance.
LiFePO resulting according to embodiment 1 4The X-ray diffracting spectrum of material is shown in Fig. 2.Demonstrate synthetic LiFePO in figure 4Good crystallinity, and contain micro-Fe 2P。LiFePO 4Good crystallinity and micro-high conductivity be Fe mutually 2The existence of P is conducive to improve LiFePO 4The high rate capability of material.
Embodiment 2
Take mol ratio as 1: 1: 1 ferrous oxalate, ammonium dihydrogen phosphate, lithium carbonate be as initial raw materials, above-mentioned raw material carried out mechanical ball milling in medium-acetone, Ball-milling Time is 3 hours.With the oven dry under 100 ℃ in drying box of ball milling product, then will dry afterproduct presintering 2 hours under 350 ℃ of conditions in nitrogen atmosphere.To the ball mill grinding of presintering product, then in containing the nitrogen and hydrogen mixture atmosphere of a small amount of hydrogen, calcining is 15 hours under 600 ℃, then calcines under 700 ℃ 5 hours again, obtains substantially carbon-free but contains a small amount of Fe 2The LiFePO of P and FeP 4Material.This material has good high magnification and ultra-high magnifications charge-discharge characteristic as anode material for lithium-ion batteries.
Embodiment 3
Take mol ratio as 1: 1: 1 ferrous oxalate, ammonium dihydrogen phosphate, lithium nitrate be as raw material, employing and metal cation mol ratio are that the citric acid of 1: 2 is that carbon source is carbon source, above-mentioned initial raw materials is dissolved in distilled water, adopt blender to stir under 80 ℃ until form gel, to the oven dry under 120 ℃ in drying box of this gel.Xerogel is mixed with appropriate conductive agent ball milling, then with this ball milling product in containing the argon hydrogen mixed atmosphere of a small amount of hydrogen, calcining is 16 hours under 600 ℃, and then calcining 2 hours under 750 ℃, synthesizes LiFePO 4Material.Resulting materials has good high magnification and ultra-high magnifications charge-discharge characteristic as lithium ion battery electrode material.
Embodiment 4
Take mol ratio as 1: 1: 1 ferrous oxalate, ammonium dihydrogen phosphate, lithium carbonate be as raw material, adopting with the metal cation mol ratio is that the ethylene glycol of 2: 1 is carbon source, above-mentioned raw material is carried out mechanical ball milling in ethanol medium, Ball-milling Time is 3 hours.Then to the ball milling product in drying box through 100 ℃ of oven dry.Again this ball milling product was calcined 20 hours under 550 ℃, and then in containing the nitrogen and hydrogen mixture atmosphere of a small amount of hydrogen through 750 ℃ of calcinings 2 hours, synthetic LiFePO 4Material.Gained LiFePO 4Material contains a small amount of carbon coated and Fe 2P, this material has good high magnification and ultra-high magnifications charge-discharge characteristic as lithium ion battery electrode material.
Embodiment 5
Take mol ratio as 1: 1: 1 ferrous oxalate, ammonium dihydrogen phosphate, lithium carbonate be as raw material, adopting with the metal cation mol ratio is that the ethylene glycol of 2: 1 is carbon source, above-mentioned raw material is carried out mechanical ball milling in ethanol medium, Ball-milling Time is 4 hours.Then to the ball milling product in drying box through 100 ℃ of oven dry.After should drying again the ball milling product in nitrogen atmosphere through 300 ℃ of presintering 5 hours, then in containing the nitrogen and hydrogen mixture atmosphere of a small amount of hydrogen through 750 ℃ of calcinings 2 hours, then calcining 12 hours under 600 ℃, synthetic LiFePO 4Material.Gained LiFePO 4Material contains a small amount of carbon coated and Fe 2P, this material has good high magnification and ultra-high magnifications charge-discharge characteristic as lithium ion battery electrode material.
Embodiment 6
Measure the LiFePO of embodiment 1 4The discharge capacity of material under different multiplying
2025 type simulated batteries are adopted in this test, take lithium as to electrode, and the LiPF take electrolyte as 1mol/L 6The mixed solution of ethylene carbonate EC/ dimethyl carbonate DMC (EC and DMC adopt the equal-volume ratio), barrier film adopts the Celgard2300 polypropylene porous film.LiFePO in positive electrode 4: graphite and acetylene black conductor: the ratio of PVDF binding agent is 75: 15: 10.Charging/discharging voltage scope 2.2-4.2V, the charging current under different discharge-rates is 0.1C (wherein 1C=170mA/g).
LiFePO 4Through the activation of the several circulations of preliminary examination, capacity reaches 165mAh/g to material under 0.1C, near its theoretical capacity.Its capacity under 1C, 5C, 10C and 20C discharge-rate reaches and reaches respectively 140,120,110 and 100mAh/g.Demonstrate material and have good high rate performance.This performance has benefited from LiFePO 4Material is tiny, evenly reach finely disseminated distribution of particles, good crystallinity and contain the Fe of micro-high conductivity 2P and FeP phase.
Comparative Examples
The acquisition of persursor material is identical with embodiment 1, and under identical atmosphere, respectively through (a) 600 ℃ calcining 20 hours, (b) 700 ℃ of calcinings are 4 hours, (c) 700 ℃ of calcinings 10 hours and (d) 800 ℃ of calcinings prepared LiFePO in 2 hours 4Material.
Above-mentioned material is scanned respectively with ESEM, the SEM pattern be shown in (a), (b), (c) of Fig. 4 and (d) in.Analyzing the SEM pattern can find out, through 600 ℃ of calcinings 20 hours and 700 ℃ of LiFePO that calcining obtained in 4 hours 4The reunion degree of material ((a) and (b)) is very large, the LiFePO that obtained in 2 hours through 800 ℃ of calcinings 4The particle size distribution of material (d) is very inhomogeneous, and the primary particle size is very large, and the part particle even substantially exceeds 2 μ m, and is larger after the part particle agglomeration, and this is unfavorable for that all material obtains good high rate capability.Through 700 ℃ of calcinings 10 hours (c) with first failed macroscopic obvious difference through 700 ℃ of materials of calcining 4 hours (embodiment 1) on the SEM pattern again through 600 ℃ of calcinings 20 hours, but learn the former Fe according to X diffraction Rietveld refine result 2P content is 2.5 % by weight, the latter's Fe 2P content is 4.3 % by weight.In particle size and under the condition that does not have obviously to distinguish that distributes, improve Fe 2P content is conducive to LiFePO from 2.5 % by weight to 4.3 % by weight 4Material obtains better high magnification and ultra-high magnifications charge-discharge performance.
Fig. 5 shows above-mentioned LiFePO 4Material (a), (b), (c) and (d) discharge capacity under different discharge-rates.Electrochemical test method as described in example 6 above.Comparison diagram 3 and Fig. 5 have illustrated and have adopted the synthetic LiFePO of associating alternating temperature calcining that puts down in writing in the present invention 4The chemical property of material is all much higher than adopting the synthetic capacity of one-step calcination under variant discharge-rate.
Following table has been summed up the performance parameter of embodiment 1 and Comparative Examples (a), (b), (c) and material (d)
Figure BDA0000060929330000091
Can clearly be seen that the LiFePO that obtains by the inventive method from above embodiment and table 4Anode material for lithium-ion batteries has effectively guaranteed the crystallinity of LiFePO4 by employing calcining of long period at relatively low temperature, and control its particle and have less size and good dispersiveness, the calcining of uniting the short period under high-temperature relatively, reach original position and introduce appropriate high conductivity Fe2P/FeP phase, and control again that particle size is not obvious grows up, thereby realized simultaneously good crystallinity, suitable particle size and good dispersed and suitable Fe 2The textural association of P/FeP content.Therefore, the LiFePO of the inventive method acquisition 4Anode material for lithium-ion batteries has been realized better charge-discharge power performance, high magnification and ultra-high magnifications performance, and is such as shown in Figure 5.

Claims (20)

1. the preparation method of an anode material for lithium-ion batteries comprises the following steps:
(1) provide the presoma of anode material for lithium-ion batteries;
(2) this presoma is carried out alternating temperature and unite calcining;
Wherein, described alternating temperature is united calcining and is comprised this presoma is implemented at least twice calcination process that carries out under different temperatures in the temperature range of 300-900 ℃,
Wherein, in described twice calcination process, the temperature of calcining is 300～750 ° of C for the first time, and the temperature of calcining is 600～900 ° of C for the second time; And
Wherein, the time of calcining is 0.5～25 hour for the first time, and the time of calcining is 0.5～15 hour for the second time.
2. according to claim 1 method, wherein, the temperature of calcining is 400～700 ° of C for the first time.
3. according to claim 2 method, wherein, the temperature of calcining is 500～650 ° of C for the first time.
4. according to claim 1 method, wherein, the temperature of calcining is 600～800 ° of C for the second time.
5. according to claim 4 method, wherein, the temperature of calcining is 650～750 ° of C for the second time.
6. according to claim 1 method, wherein, the time of calcining is 5～20 hours for the first time.
7. according to claim 1 method, wherein, the time of calcining is 1～15 hour for the second time.
8. the preparation method of an anode material for lithium-ion batteries comprises the following steps:
(1) provide the presoma of anode material for lithium-ion batteries;
(2) this presoma is carried out alternating temperature and unite calcining;
Wherein, described alternating temperature is united calcining and is comprised this presoma is implemented at least twice calcination process that carries out under different temperatures in the temperature range of 300-900 ℃,
Wherein, in described twice calcination process, the temperature of calcining is 900 ° of C of 600 – for the first time, and the temperature of calcining is 300～750 ° of C for the second time; And
Wherein, the time of calcining is 0.5～15 hour for the first time, and the time of calcining is 0.5～25 hour for the second time.
9. according to claim 8 method, wherein, the temperature of calcining is 600～800 ° of C for the first time.
10. according to claim 9 method, wherein, the temperature of calcining is 650～750 ° of C for the first time.
11. method according to claim 8, wherein, the temperature of calcining is 400～700 ° of C for the second time.
12. method according to claim 11, wherein, the temperature of calcining is 500～650 ° of C for the second time.
13. method according to claim 8, wherein, the time of calcining is 1～15 hour for the first time.
14. method according to claim 8, wherein, the time of calcining is 5～20 hours for the second time.
15. the method for any one according to claim 1～14, wherein, described alternating temperature is united calcining and is carried out in inert atmosphere or reducing atmosphere.
16. the method for any one according to claim 1～14 wherein, before alternating temperature associating calcining step, is carried out presintering in the temperature range of 250～400 ℃ to described presoma.
17. the method for any one according to claim 1～14, wherein, the described step that presoma is provided comprises provides source of iron, phosphorus source, lithium source and optional carbon source, then process by solid phase mechanical activation method, solid-state direct mechanical ball-milling method, sol-gal process or spray drying process, obtain thus presoma.
18. the method for any one according to claim 1～14, wherein said anode material for lithium-ion batteries are LiFePO 4Anode material for lithium-ion batteries.
19. the anode material for lithium-ion batteries of the method for any one preparation according to claim 1～18.
20. anode material for lithium-ion batteries according to claim 19, the average primary particle size of wherein said anode material for lithium-ion batteries is less than 500nm, and Fe 2P/FeP content is 3.5～10 % by weight.
CN2011101231156A 2011-05-13 2011-05-13 Preparation method for lithium ion battery cathode materials Active CN102225753B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN2011101231156A CN102225753B (en) 2011-05-13 2011-05-13 Preparation method for lithium ion battery cathode materials

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN2011101231156A CN102225753B (en) 2011-05-13 2011-05-13 Preparation method for lithium ion battery cathode materials

Publications (2)

Publication Number Publication Date
CN102225753A CN102225753A (en) 2011-10-26
CN102225753B true CN102225753B (en) 2013-06-26

Family

ID=44806767

Family Applications (1)

Application Number Title Priority Date Filing Date
CN2011101231156A Active CN102225753B (en) 2011-05-13 2011-05-13 Preparation method for lithium ion battery cathode materials

Country Status (1)

Country Link
CN (1) CN102225753B (en)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6216965B2 (en) 2012-01-31 2017-10-25 住友大阪セメント株式会社 Electrode material, electrode plate, lithium ion battery, method for producing electrode material, and method for producing electrode plate
TWI507353B (en) * 2013-04-15 2015-11-11 Formosa Biomedical Technology Corp Process for producing lvf/c composite material and use the same
CN103682336A (en) * 2013-12-23 2014-03-26 复旦大学 Method for improving conductivity of pure lithium iron phosphate anode material
CN104882605B (en) * 2015-05-14 2017-03-15 王海峰 A kind of preparation method of lithium ion battery material LiFePO 4
CN111370682A (en) * 2020-03-26 2020-07-03 四川青源新材料有限公司 Lithium ion battery anode material precursor, anode material and preparation method
CN114843487B (en) * 2022-06-01 2023-08-01 湖北亿纬动力有限公司 Lithium iron phosphate material, preparation method thereof and lithium ion battery
CN114852986B (en) * 2022-07-07 2022-10-25 楚能新能源股份有限公司 Preparation method of high-compaction lithium iron phosphate and lithium iron phosphate prepared by same

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101950801A (en) * 2010-09-21 2011-01-19 新疆金盛科达有色金属新材料有限责任公司 Preparation method of positive electrode material LiFePO4/C of lithium ion battery

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101950801A (en) * 2010-09-21 2011-01-19 新疆金盛科达有色金属新材料有限责任公司 Preparation method of positive electrode material LiFePO4/C of lithium ion battery

Also Published As

Publication number Publication date
CN102225753A (en) 2011-10-26

Similar Documents

Publication Publication Date Title
KR101964726B1 (en) Spherical or spherical-like lithium ion battery cathode material and preparation method and application thereof
Sun et al. Mesoporous Li4Ti5O12 nanoclusters as high performance negative electrodes for lithium ion batteries
CN101162776B (en) Lithium iron phosphate suitable for high multiplying power electrokinetic cell and method for producing the same
Li et al. Uniform Li1. 2Ni0. 13Co0. 13Mn0. 54O2 hollow microspheres with improved electrochemical performance by a facile solvothermal method for lithium ion batteries
Alsamet et al. Synthesis and characterization of nano-sized LiFePO4 by using consecutive combination of sol-gel and hydrothermal methods
CN102225753B (en) Preparation method for lithium ion battery cathode materials
Gao et al. Combustion-derived nanocrystalline LiMn2O4 as a promising cathode material for lithium-ion batteries
CN106876705B (en) Preparation method of in-situ synthesized carbon/carbon nanotube coated lithium iron phosphate composite material
Zhang et al. Convenient and high-yielding strategy for preparing nano-ZnMn2O4 as anode material in lithium-ion batteries
CN101587950A (en) Micron single crystal granular anode material of lithium ion battery
CN109607505A (en) A kind of preparation method for the LiFePO4 improving cryogenic property
CN101847722A (en) High-performance lithium ion battery cathode material and preparation method thereof
WO2011009231A1 (en) Method for preparing carbon-coated positive material of lithium ion battery
CN102367170A (en) Core shell type carbon cladding nano-scale lithium iron phosphate compound cathode material and preparation method thereof
CN103094550A (en) Preparation method of lithium-rich anode material
CN110589791B (en) Preparation method of tin-doped titanium pyrophosphate
CN107732176A (en) The preparation method of nano-scale lithium ion battery anode material
CN108807928B (en) Synthesis of metal oxide and lithium ion battery
Wu et al. Construction of submicron-sized LiFe0. 4Mn0. 6PO4/C enwrapped into graphene framework for advanced Li-storage
CN103413918B (en) A kind of synthetic method of anode material for lithium ion battery cobalt phosphate lithium
Kong et al. Synthesis of lithium rich layered oxides with controllable structures through a MnO2 template strategy as advanced cathode materials for lithium ion batteries
Dai et al. Ultrathin 3 V Spinel Clothed Layered Lithium‐Rich Oxides as Heterostructured Cathode for High‐Energy and High‐Power Li‐ion Batteries
Zhou et al. Hierarchical LiNi 0.5 Mn 1.5 O 4 micro-rods with enhanced rate performance for lithium-ion batteries
Sadeghi et al. Surface modification of LiMn2O4 for lithium batteries by nanostructured LiFePO4 phosphate
Jiang et al. Multiple regulation of surface engineering for lithium-rich layered cathode materials via one-step strategy

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