CN102655231B - A kind of method preparing high power performance anode material for lithium-ion batteries LiMn2O4 - Google Patents

A kind of method preparing high power performance anode material for lithium-ion batteries LiMn2O4 Download PDF

Info

Publication number
CN102655231B
CN102655231B CN201210139968.3A CN201210139968A CN102655231B CN 102655231 B CN102655231 B CN 102655231B CN 201210139968 A CN201210139968 A CN 201210139968A CN 102655231 B CN102655231 B CN 102655231B
Authority
CN
China
Prior art keywords
limn
lithium
spherical
micron level
anode material
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
Application number
CN201210139968.3A
Other languages
Chinese (zh)
Other versions
CN102655231A (en
Inventor
邓远富
周玉波
施志聪
陈申
陈国华
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.)
Guangzhou HKUST Fok Ying Tung Research Institute
Original Assignee
Guangzhou HKUST Fok Ying Tung Research Institute
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 Guangzhou HKUST Fok Ying Tung Research Institute filed Critical Guangzhou HKUST Fok Ying Tung Research Institute
Priority to CN201210139968.3A priority Critical patent/CN102655231B/en
Publication of CN102655231A publication Critical patent/CN102655231A/en
Application granted granted Critical
Publication of CN102655231B publication Critical patent/CN102655231B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

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

Landscapes

  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention discloses a kind of height ratio capacity, high rate capability and cycle performance, cheap, environmental friendliness and constitutionally stable multi-pore micron level spherical power battery LiMn 2o 4the novel processing step of positive electrode, belongs to li-ion electrode materials preparing technical field.The present invention is characterized in: utilize spheric manganese carbonate self as template and insert in conjunction with the low salt that melts altogether the novel synthetic low-temperature growth LiMn combined 2o 4material.LiMn prepared by the method 2o 4material morphology is regular, purity is high, tap density is large, specific capacity is high, good cycle have excellent high rate performance.This material 2,10 and the rushing of 20C/discharging condition under, the specific capacity of this material is respectively 118,106 and 98mAh/g.Circulate after 500 times, its capability retention > 80%.Relative to traditional solid phase method, the method utilizes shirtsleeve operation successfully to control the pattern of product, improves the tap density of product, purity, specific capacity and high rate performance, is the novel developing direction of preparation high-performance positive electrode.

Description

A kind of method preparing high power performance anode material for lithium-ion batteries LiMn2O4
Technical field
The present invention relates to a kind of novel processing step of high performance lithium ion battery anode active material.Particularly there is the preparation of the LiMn2O4 of micron-size spherical pore space structure and high rate capability.
Background technology
The storage of the energy is making full use of earth resource with conversion, improves the aspects such as the existing and following living environment of the mankind and plays an important role.As the storage of the energy and a kind of important way of conversion-chemical power source is widely used in people's daily life is produced.Along with scientific technological advance, the requirement of people's living environment quality is more and more high, and electric automobile is because of the advantage of " zero discharge " when it uses, and society is increasingly urgent to its demand.Lithium ion battery because voltage is high, capacity is high, volume is little, the special performance such as lightweight, memory-less effect, have again have extended cycle life, feature that security performance is good, at 3 C (portable computer, communication and consumer electronics) market, electric automobile, space technology, national defense industry etc. are many-sided illustrates wide application prospect and potential great economic benefit, therefore, lithium ion battery is the focus in recent years paid close attention to and study.But, the final performance of battery and the performance of electrode material closely related, the progress of battery material is depended in the progress of battery to a great extent.Therefore, low cost prepare high-energy-density, high power density, high security, particularly environmentally safe green battery material be the emphasis of research in current and following a period of time.
Positive electrode is the key factor determining performance of lithium ion battery, is therefore a pith of lithium ion battery material research to the research and development of positive electrode active materials.The research work of current people to positive electrode active materials mainly concentrates on stratiform LiCoO 2, LiNiO 2, LiFePO 4with spinelle LiMn 2o 4on.LiCoO 2shortcoming is that actual specific capacity is only about 50% of theoretical capacity, and the utilance of cobalt is low, and overcharge resistant ability is poor, and under comparatively high charge voltage, specific capacity reduces rapidly.In addition, add cobalt resource scarcity, the factor that price is high, therefore, decrease the scope of application of cobalt series lithium ion battery to a great extent, be especially restricted in electric automobile and large-scale redundant electrical power; For LiNiO 2synthesis, sintering temperature and sintering atmosphere are the Li easily forming non-stoichiometric in synthesis 1-xni 1+xo 2, the oxygen of release may react with electrolyte, causes safety problem; LiFePO 4major defect is poorly conductive, and tap density is lower, not low temperature resistant.With stratiform LiCoO 2, LiNiO 2compare, spinelle LiMn 2o 4although theoretical specific capacity is 148 mAh/g, two discharge platforms had are respectively at 3.95 and 4.15 V, relatively high and stable.Meanwhile, manganese (Mn) rich reserves, especially the promoter manganese of China accounts for first of countries in the world.Therefore LiMn is developed 2o 4electrode material, can reduce battery cost greatly.LiMn 2o 4have stable three-dimensional spinel structure, wherein the lithium of more than 80% can allow deintercalation out, also can not cause structural collapse; From a security perspective, LiMn is used 2o 4the lithium ion battery overcharging resisting discharge performance that positive pole is made is better, even without the need to protective circuit.Therefore, it is considered to a kind of very promising positive electrode active materials.LiMn2O4 is the decomposition of decay as Mn of capacity in cyclic process as the subject matter that positive electrode exists, Jahn-the decomposition of Teller effect and electrolyte, the change of structure, causes this material high rate performance poor, limits its application.The preparation method of material and the performance of pattern on material have very large impact, therefore develop new synthetic method the impact of system research novel method for synthesizing on the correlated performance of material is necessary.Based on above true and LiMn 2o 4the potential application of material, the invention discloses a kind of height ratio capacity, high rate capability and cycle performance, the multi-pore micron level spherical power battery LiMn that cheap, environmental friendliness, Stability Analysis of Structures and security performance are good 2o 4the novel processing step of positive electrode.
The present invention first adopts simple solvent heat or water heat transfer microspheroidal MnCO 3material, then passes through certain mixing method by a certain percentage by MnCO 3with the mixing of eutectic lithium source, under uniform temperature and condition, the spherical LiMn of multi-pore micron level is prepared in calcining 2o 4material.LiMn prepared by the method 2o 4material morphology is regular, purity is high, tap density is large, specific capacity is high, good cycle have excellent high rate performance, is desirable high-energy-density power lithium ion cell positive material.。Electro-chemical test shows, LiMn prepared by the method 2o 4the specific discharge capacity of material 1 C reaches 125 mAh/g, and after circulation 100 circle, capacity still reaches 114 mAh/g, capability retention > 90%.At 2 C, under the rushing of 5 C, 10 C, 20 C, 30 C and 50 C/discharging condition, the specific capacity of this material is respectively 118,112,106,98,88 and 70 mAh/g.Under 2,10 and 20 C multiplying powers, after 500 circle circulations, capability retention is respectively 82%, 91% and 80%.Present invention process is simple, easy to operate, to experimental situation without particular/special requirement, pollution-free, is suitable for enlarged reproduction.
Summary of the invention
The object of this invention is to provide a kind of height ratio capacity, high rate capability and good circulation performance, the multi-pore micron level spherical power cell positive material that cheap, environmental friendliness, Stability Analysis of Structures and security performance are good.
Another object of the present invention is to provide described multi-pore micron level spherical structure LiMn 2o 4the novel processing step of positive electrode.
The method realizing above-mentioned purpose employing utilizes spheric manganese carbonate presoma self as template and inserts in conjunction with the low salt that melts altogether the novel synthetic combined.
Preparation technology's key step of the present invention is as follows:
Step 1, manganese salt, precipitation reagent, solvent, surfactant and additive to be mixed, wherein manganese salt: the mol ratio of precipitation reagent is 1:1 to 1:9;
Step 2, by step 1 gained mixture 25-under 55 DEG C of waters bath with thermostatic control stir 1 hour, formed uniform solution;
Step 3, the solution of step 2 gained is transferred in the reactor of polytetrafluoroethylene, in 120-at 220 DEG C, reacting 12-48 hours;
Step 4, centrifugal for the product of step 3 gained or isolated by filtration is respectively washed 3 times with distilled water and absolute ethyl alcohol, vacuumize 12 hours at 80 DEG C;
Step 5, two kinds of lithium salts to be mixed according to certain ratio, prepare Eutectic molten salt system;
Step 6, step 4 products therefrom and step 5 products therefrom to be mixed according to a certain percentage, near eutectic point 200-calcining 2 at 700 DEG C-4 hours, then-at 900 DEG C, calcine 6-600 and 12 hours, obtain product LiMn 2o 4;
Step 7, by obtained LiMn 2o 4product XRD, SEM and TEM (HTEM) characterize, and carry out electrochemical property test to this sample.
Manganese salt used in the present invention is one in manganese chloride, manganese nitrate, manganese sulfate or its salt-mixture.
Precipitation reagent used in the present invention is carbonic hydroammonium, the one of urea or its mixture.
Surfactant used in the present invention is one or its mixture of PEG400, Macrogol 600, polyethylene glycol-800, cetomacrogol 1000 and Macrogol 2000.
Solvent used in the present invention is water, ethanol, ethylene glycol, 1,2-and propylene glycol one or its mixture.
Eutectic lithium salts used in the present invention is LiOHH 2o, LiCl, LiNO 3, Li 2cO 3in two kinds.
Advantage of the present invention and positive effect are:
Present invention process is simple, easy to operate, to experimental situation without particular/special requirement, pollution-free, is suitable for enlarged reproduction;
Solvent thermal reaction is prepared presoma pattern and is easy to control, and by calcining after this presoma together fused salt mixing, both can make the LiMn of preparation 2o 4positive electrode keeps the spherical structure of presoma, and the gas produced in calcination process can be utilized again to make the LiMn of preparation 2o 4positive electrode has pore space structure.The spherical structure of regular appearance is conducive to the tap density improving material, and pore space structure is conducive to the contact of electrolyte and active material, thus improves material circulation performance and high rate performance.
Adopt Eutectic molten salt to insert the preparation method of spherical hole manganese carbonate presoma, avoid and run into lithium source in conventional solid-state method synthetic lithium manganate material and mix uneven problem with manganese source, thus obtain the high product of purity.
The material crystalline degree of synthesis is high, and the primary particle being 100 nm by particle diameter is agglomerated into micron-sized spherical pore space structure, and pattern is homogeneous and particle size distribution range is narrow, ensures strong mechanical property.
This material, as the positive electrode active materials of lithium rechargeable battery, has higher charging and discharging capacity, excellent cycle performance and high rate performance, is desirable high-energy-density power lithium-ion battery positive electrode, has good practical value.
Accompanying drawing explanation
Fig. 1 is presoma MnCO 3xRD figure;
Fig. 2 is presoma MnCO 3sEM figure;
Fig. 3 is product LiMn 2o 4xRD figure;
Fig. 4 is product LiMn 2o 4sEM figure;
Fig. 5 is product LiMn 2o 4tEM figure;
Fig. 6 is product LiMn 2o 4charging and discharging curve figure;
Fig. 7 is product LiMn 2o 4cycle performance performance map;
Fig. 8 is product LiMn 2o 4high rate performance figure.
Embodiment
Being below specific embodiment, introducing content of the present invention in detail, providing embodiment to be for the ease of understanding the present invention, is never restriction invention.
Spherical LiMn provided by the present invention 2o 4material uses as positive electrode active materials in preparing in lithium ion battery.
embodiment 1
Take 2.969 grams of MnCl 2h 2o, is dissolved in 33 mL ethylene glycol solutions, more dropwise adds 1.5-the Macrogol 2000 of 2.0 g, and 50 oCunder condition of water bath heating, limit is stirred and is slowly added 2.70 grams of urea (manganous chloride: the mol ratio of urea is 1:3) below, maintains this temperature and continues stirring 1 hour.This mixed solution is transferred in the reactor of 50 mL polytetrafluoroethylene linings, reacts 12 hours at 200 DEG C.Question response still is cooled to room temperature, is separated by gained sedimentation and filtration and uses deionized water and absolute ethyl alcohol respectively to clean 3 times, vacuumize 12 hours at 80 DEG C, obtains the spherical MnCO of white 3presoma.
By eutectic lithium salts 0.38Li (OH) .h 2o-0.62LiNO 3mnCO spherical with above-mentioned product 3presoma is incubated 3 h after fully mixing than the ratio for 1.05:2 according to amount of substance at 200 DEG C, then in 700 DEG C of calcining 8 h, obtains black product, the product obtained is made respectively elementary analysis and XRD analysis, show that product is LiMn 2o 4.
With the spherical LiMn prepared under above-mentioned condition 2o 4the electrolyte adapted for positive electrode active materials and coupling and barrier film, be assembled into CR2025 type battery.3.2-under the discharge and recharge condition of 4.4 V, 0.1 C, the first circle specific discharge capacity of this material is 131 mAh/g.At 2 C, under the rushing of 5 C, 10 C, 20 C, 30 C and 50 C/discharging condition, the specific capacity of this material is respectively 118,112,106,98,88 and 70 mAh/g.Under 2,10 and 20 C multiplying powers, after 500 circle circulations, capability retention is respectively 82%, 91% and 80%.Result shows, this material has excellent cycle performance and high rate performance.
embodiment 2
Take 2.969 grams of MnCl 2h 2o, is dissolved in 33 mL ethylene glycol solutions, more dropwise adds 1.5-the Macrogol 2000 of 2.0 g, and 50 oCunder condition of water bath heating, limit is stirred and is slowly added 2.70 grams of urea (manganous chloride: the mol ratio of urea is 1:3) below, maintains this temperature and continues stirring 1 hour.This mixed solution is transferred in the reactor of 50 mL polytetrafluoroethylene linings, reacts 24 hours at 200 DEG C.Question response still is cooled to room temperature, is separated by gained sedimentation and filtration and uses deionized water and absolute ethyl alcohol respectively to clean 3 times, vacuumize 12 hours at 80 DEG C, obtains the spherical MnCO of white 3presoma.
By eutectic lithium salts 0.38LiOHH 2o-0.62LiNO 3with above-mentioned product MnCO 3after ratio according to 1.1: 2 fully mixes, at 200 DEG C, be incubated 3 h, then in 700 DEG C of calcining 8 h, obtain black product, the product obtained is made elementary analysis and XRD analysis respectively, show that product is LiMn 2o 4.
With the spherical LiMn prepared under above-mentioned condition 2o 4the electrolyte adapted for positive electrode active materials and coupling and barrier film, be assembled into CR2025 type battery.3.2-under the discharge and recharge condition of 4.4 V, 0.1 C, the first circle discharge capacity of this material is 120 mAh/g, and in 5 C rate charge-discharge situations, specific capacity is 107 mAh/g, and after circulation 500 circle, capacity is still up to 85 mAh/g; Discharge capacity under 10 C multiplying powers reaches 103 mAh/g.Result shows, this material has excellent cycle performance and high rate performance.
embodiment 3
Take 2.969 grams of MnCl 2h 2o, is dissolved in 33 mL ethylene glycol solutions, more dropwise adds 1.5-the Macrogol 2000 of 2.0 g, and 50 oCunder condition of water bath heating, limit is stirred and is slowly added 2.70 grams of urea (manganous chloride: the mol ratio of urea is 1:3) below, maintains this temperature and continues stirring 1 hour.This mixed solution is transferred in the reactor of 50 mL polytetrafluoroethylene linings, reacts 12 hours at 120 DEG C.Question response still is cooled to room temperature, is separated by gained sedimentation and filtration and uses deionized water and absolute ethyl alcohol respectively to clean 3 times, vacuumize 12 hours at 80 DEG C, obtains the spherical MnCO of white 3presoma.
By eutectic lithium salts 0.38LiOHH 2o-0.62LiNO 3with above-mentioned product MnCO 3after fully mixing according to the ratio of 1:2, at 200 DEG C, be incubated 3 h, then in 700 DEG C of calcining 8 h, obtain black product, the product obtained is made elementary analysis and XRD analysis respectively, show that product is LiMn 2o 4.
With the spherical LiMn prepared under above-mentioned condition 2o 4the electrolyte adapted for positive electrode active materials and coupling and barrier film, be assembled into CR2025 type battery.3.2-under the discharge and recharge condition of 4.4 V, 0.1 C, the first circle discharge capacity of this material is 120 mAh/g, and under 1 C rate charge-discharge condition, its specific capacity is 118 mAh/g, and after circulation 100 circle, capacity is still up to 105 mAh/g.
embodiment 4
Take 2.969 grams of MnCl 2h 2o, be dissolved in 33 mL ethylene glycol solutions, more dropwise add 1.5-the Macrogol 2000 of 2.0 g, under 50 DEG C of condition of water bath heating, limit is stirred and is slowly added 2.70 grams of urea (manganous chloride: the mol ratio of urea is 1:3) below, maintains this temperature and continues stirring 1 hour.This mixed solution is transferred in the reactor of 50 mL polytetrafluoroethylene linings, reacts 12 hours at 200 DEG C.Question response still is cooled to room temperature, is separated by gained sedimentation and filtration and uses deionized water and absolute ethyl alcohol respectively to clean 3 times, vacuumize 12 hours at 80 DEG C, obtains the spherical MnCO of white 3presoma.
By eutectic lithium salts 0.74LiOHH 2o-0.26Li 2cO 3with above-mentioned product MnCO 3after fully mixing according to the ratio of 1.05:2, at 420 DEG C, be incubated 3 h, then in 700 DEG C of calcining 8 h, obtain black product, the product obtained is made elementary analysis and XRD analysis respectively, show that product is LiMn 2o 4.
With the spherical LiMn prepared under above-mentioned condition 2o 4the electrolyte adapted for positive electrode active materials and coupling and barrier film, be assembled into CR2025 type battery.3.2-under the discharge and recharge condition of 4.4 V, 0.1 C, the first circle discharge capacity of this material is 116 mAh/g, and under 1 C rate charge-discharge condition, its specific capacity is 112 mAh/g, and after circulation 100 circle, capacity is still up to 100 mAh/g.
MnCl in embodiment 1 2h 2the thing mass ratio of O and urea is 1:3, in 200 DEG C of solvent thermal reactions 12 hours, and the presoma microballoon MnCO obtained 3through XRD analysis (Fig. 1), the diffraction peak intensity in figure is very strong, and the position at peak and standard spectrogram (JCPDS Card No.00-04-1472) coincide.The scanning electron microscope analysis (Fig. 2) of this sample, result shows, this presoma is the porous spherical structure of diameter about 1 microns.This presoma and eutectic lithium salts ground and mixed is even, calcine the product that obtains under certain condition through XRD analysis (Fig. 3), coincide with standard spectrogram (JCPDS Card No.-35-0782).The ESEM of this sample and transmission electron microscope (Fig. 4) show this product to be diameter are the LiMn of the multi-pore micron level spherical structure of the particle aggregation of about 100 nm 2o 4.
By embodiment 1-the LiMn of 4 preparations 2o 4material, conductive agent acetylene black and Kynoar (PVDF) stir or ball milling mixing according to the ratio of mass ratio 8:1:1, add appropriate N-methyl pyrrolidone solvent, with the LiPF containing 1 mol/L 6eC-DEC-DMC (volume ratio is 1:1:1) be electrolyte, polypropylene porous film is barrier film, and metal lithium sheet is to electrode, in argon gas glove box, form button cell.Discharge and recharge instrument carries out charge-discharge performance test.
Sample prepared by example 1 shows excellent chemical property, first circle discharge capacity under the discharge and recharge condition of its 0.1 C is 131 mAh/g, at 2 C, and 5 C, 10 C, under the rushing of 20 C, 30 C and 50 C/discharging condition, the specific capacity of this material is respectively 118,112,106,98,88 and 70 mAh/g.Under 2,10 and 20 C multiplying powers, after 500 circle circulations, capability retention is respectively 82%, 91% and 80%.Result shows cycle performance and the high rate performance of this material excellence
Above-mentioned concrete execution mode is optimum execution mode of the present invention, the especially ratio of manganese salt and urea, the time of solvent thermal reaction, temperature, the selection of eutectic lithium salts system, and the selection of corresponding calcining heat.But can not limit claim of the present invention, other is any does not deviate from technical scheme of the present invention and is included within protection scope of the present invention.

Claims (8)

1. a reactant self prepares the spherical LiMn of high performance multi-pore micron level as template in conjunction with Eutectic molten salt insertion 2o 4the preparation method of anode material for lithium-ion batteries, is characterized in that:
(1) first presoma template MnCO is synthesized 3, by eutectic lithium salts and presoma MnCO 3(1+ in molar ratio x)/2 mix, wherein x=0 ~ 0.05;
(2) be raised to 200-400 DEG C with the heating rate of 5 ~ 10 DEG C/min, keep 2-4 hour; Being raised to 600-900 DEG C with same heating rate, keeping 6-12 hour, products therefrom is naturally cooled to room temperature, is gained end product LiMn after taking out 2o 4;
Wherein, solvent-thermal method is adopted to prepare microspheroidal MnCO 3, its preparation process is as follows:
(1) manganese source, carbonate, solvent and stabilizer are mixed, wherein the ratio of manganese source and carbonate is 1:1-1:9;
(2) the above-mentioned solution mixed is transferred in the reactor of 50 mL polytetrafluoroethylene, at 120-220 DEG C, reacts 12-48 hours;
(3) product of step (2) gained and solution are poured out, filter, then respectively wash 2-5 time with distilled water and ethanol, at 50-80 DEG C of vacuumize 9-12 hour, obtain porous spherical MnCO 3presoma.
2. the spherical LiMn of multi-pore micron level according to claim 1 2o 4the preparation method of anode material for lithium-ion batteries, is characterized in that: described MnCO 3there is the structure that the multi-pore micron level of nano particle reunion is spherical.
3. the spherical LiMn of multi-pore micron level according to claim 1 2o 4the preparation method of anode material for lithium-ion batteries, is characterized in that: adopt MnCO 3the LiMn that self prepares as soft template and in conjunction with the method that eutectic lithium salts inserts 2o 4there is the structure that the multi-pore micron level of nano particle reunion is spherical.
4. the spherical LiMn of multi-pore micron level according to claim 1 2o 4the preparation method of anode material for lithium-ion batteries, is characterized in that: carbonate used is carbonic hydroammonium.
5. the spherical LiMn of multi-pore micron level according to claim 1 2o 4the preparation method of anode material for lithium-ion batteries, is characterized in that: solvent used is one in water, ethanol, ethylene glycol or its mixture.
6. the spherical LiMn of multi-pore micron level according to claim 1 2o 4the preparation method of anode material for lithium-ion batteries, is characterized in that: stabilizer used is one in PEG400, Macrogol 600, polyethylene glycol-800, Macrogol 2000 or its mixture.
7. the spherical LiMn of multi-pore micron level according to claim 1 2o 4the preparation method of anode material for lithium-ion batteries, is characterized in that: manganese source used is one in manganese nitrate, manganese sulfate, manganese chloride or its mixture.
8. the spherical LiMn of multi-pore micron level according to claim 1 2o 4the preparation method of anode material for lithium-ion batteries, is characterized in that: the eutectic lithium salts of employing is Li (OH), LiNO 3, LiCl or Li 2cO 3in two or more, its eutectic point temperature is 150-500 DEG C.
CN201210139968.3A 2012-05-08 2012-05-08 A kind of method preparing high power performance anode material for lithium-ion batteries LiMn2O4 Expired - Fee Related CN102655231B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201210139968.3A CN102655231B (en) 2012-05-08 2012-05-08 A kind of method preparing high power performance anode material for lithium-ion batteries LiMn2O4

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201210139968.3A CN102655231B (en) 2012-05-08 2012-05-08 A kind of method preparing high power performance anode material for lithium-ion batteries LiMn2O4

Publications (2)

Publication Number Publication Date
CN102655231A CN102655231A (en) 2012-09-05
CN102655231B true CN102655231B (en) 2015-08-05

Family

ID=46730816

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201210139968.3A Expired - Fee Related CN102655231B (en) 2012-05-08 2012-05-08 A kind of method preparing high power performance anode material for lithium-ion batteries LiMn2O4

Country Status (1)

Country Link
CN (1) CN102655231B (en)

Families Citing this family (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102832381A (en) * 2012-09-07 2012-12-19 广州市香港科大霍英东研究院 Preparation method of high-voltage cathode material Lil+xMn3/2-yNil/2-zMy+zO4 of lithium ion battery with long service life
CN102903909A (en) * 2012-10-22 2013-01-30 中国科学院福建物质结构研究所 Manganese-cobalt-lithium oxide positive electrode material of lithium ion battery and preparation method of material
CN103633313B (en) * 2012-11-13 2016-04-06 天津锦美碳材科技发展有限公司 The preparation method of a kind of fluorographite and LiMn2O4 composite material and prepare lithium ion battery as positive electrode
CN103367739A (en) * 2013-07-18 2013-10-23 桂林电子科技大学 Ellipsoidal porous-structured lithium manganate or nickel lithium manganate positive electrode material and preparation method thereof
CN104733706B (en) * 2013-12-23 2017-03-01 北京有色金属研究总院 A kind of preparation method of high-tap density composite positive pole
CN104362319A (en) * 2014-11-21 2015-02-18 东莞市迈科科技有限公司 Preparation method of porous tin-carbon composite negative material
CN105000598B (en) * 2015-05-08 2017-01-18 青岛科技大学 Method for preparing manganese carbonate hollow spheres
CN105070904B (en) * 2015-07-28 2018-03-30 厦门理工学院 Positive electrode active materials, preparation method and battery
CN105428628A (en) * 2015-12-28 2016-03-23 安徽工业大学 Preparation method of porous spherical high-voltage lithium ion battery positive electrode material
CN107369825B (en) * 2017-07-26 2020-01-10 华南理工大学 Nitrogen-doped carbon-coated manganese oxide lithium ion battery composite negative electrode material and preparation method and application thereof
CN110817965A (en) * 2018-08-07 2020-02-21 山东力盛新能源科技有限公司 Preparation method of porous microsphere sodium-ion battery positive electrode material
CN109734133B (en) * 2019-03-19 2021-04-02 浙江中金格派锂电产业股份有限公司 Preparation method of volumetric lithium manganate
CN110783568B (en) * 2019-11-04 2021-05-04 陕西科技大学 Preparation method and application of hollow carbon-coated molybdenum selenide nanostructure
CN112830524A (en) * 2019-11-22 2021-05-25 中国科学院大连化学物理研究所 Transition metal oxide positive electrode material of single crystal lithium and preparation method and application thereof
CN112342563A (en) * 2020-11-02 2021-02-09 大连理工大学 Preparation method and application of nickel self-supporting electrode loaded with ferric hydroxide and manganese carbonate

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102148359A (en) * 2010-02-08 2011-08-10 清华大学 Preparation method of lithium manganate anode active material

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102148359A (en) * 2010-02-08 2011-08-10 清华大学 Preparation method of lithium manganate anode active material

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
Preparation of spherical spinel LiMn2O4 cathode material for lithium ion batteries;Xiang Ming He,et al.;《J Solid State Electrochem》;20041215;第9卷;438-444 *
Synthesis of LiMn2O4 by molten salt technique;M. Helan·L.,et al.;《Ionics》;20090902;第16卷;227-231 *
Yuan-Li Ding,et al..Double-shelled hollow microspheres of LiMn2O4 for high-performance lithium ion batteries.《J. Mater. Chem.》.2011,第21卷9475-9479. *

Also Published As

Publication number Publication date
CN102655231A (en) 2012-09-05

Similar Documents

Publication Publication Date Title
CN102655231B (en) A kind of method preparing high power performance anode material for lithium-ion batteries LiMn2O4
CN109980219B (en) Full-gradient nickel-cobalt-manganese positive electrode material, ruthenium oxide coating material and preparation method thereof
CN100461507C (en) Making method for nano LiFePO4-carbon composite cathode material
CN104795560B (en) A kind of rich sodium P2 phase layered oxide materials and its production and use
CN1332878C (en) Prepn process of oxygen place doped lithium ferric phosphate powder
CN104993121B (en) A kind of nickel manganese blending anode material for lithium-ion batteries and preparation method thereof
CN101752562B (en) Compound doped modified lithium ion battery anode material and preparation method thereof
CN103280570B (en) Preparation method of micron-order single-crystal nickel lithium manganate anode material
CN105185954A (en) LiAlO2 coated LiNi1-xCoxO2 lithium-ion battery positive electrode material and preparation method thereof
CN102838102B (en) Preparation method of lithium iron phosphate monocrystalline nanorods
CN102386412A (en) Lithium ion battery anode Li3V2(PO4)3/C composite material and preparation method thereof
CN103078099A (en) Anode material for lithium ion cell and preparation method thereof
CN101859888A (en) Lithium manganese composite oxide for lithium battery cathode active material and preparation method thereof
CN105529439A (en) Method for preparing lithium iron phosphate by hydrothermal method and lithium iron phosphate prepared by method
CN101931073A (en) Preparation method of lithium iron phosphate/carbon composite cathode material
CN102832381A (en) Preparation method of high-voltage cathode material Lil+xMn3/2-yNil/2-zMy+zO4 of lithium ion battery with long service life
CN102339996A (en) Synthesis and performance of spherical mesoporous anode materials MnO/Mn2O3 for lithium ion battery
Liang et al. Significant improved electrochemical performance of Li (Ni1/3Co1/3Mn1/3) O2 cathode on volumetric energy density and cycling stability at high rate
CN114229921B (en) Al 2 O 3 -ZrO 2 Coated lithium-rich manganese-based positive electrode material and preparation method thereof
CN100537418C (en) Preparation method of transition element doped iron lithium phosphate powder
Xu et al. Hollow and hierarchical Li1. 2Mn0. 54Ni0. 13Co0. 13O2 micro-cubes as promising cathode materials for lithium ion battery
He et al. Synthesis and electrochemical properties of chemically substituted LiMn2O4 prepared by a solution-based gel method
CN104485441B (en) A kind of quaternary metal phosphate anode material for lithium-ion batteries and preparation method thereof
CN1255887C (en) Method of preparing positive electrode composite material of lithium ion cell contg, ferrous phosphate lithium salt-carbon
CN100527482C (en) Making method for LiFePO4-carbon composite cathode material of 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: 20150805

Termination date: 20180508