CN101935072A - Ferrous lithium sulphate fluoride as well as preparation method and application thereof - Google Patents

Ferrous lithium sulphate fluoride as well as preparation method and application thereof Download PDF

Info

Publication number
CN101935072A
CN101935072A CN2010102639492A CN201010263949A CN101935072A CN 101935072 A CN101935072 A CN 101935072A CN 2010102639492 A CN2010102639492 A CN 2010102639492A CN 201010263949 A CN201010263949 A CN 201010263949A CN 101935072 A CN101935072 A CN 101935072A
Authority
CN
China
Prior art keywords
lithium
feso
fluorosulfuric acid
ferrous
ferrous lithium
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN2010102639492A
Other languages
Chinese (zh)
Other versions
CN101935072B (en
Inventor
郭玉国
郭维
万立骏
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.)
Institute of Chemistry CAS
Original Assignee
Institute of Chemistry CAS
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 Institute of Chemistry CAS filed Critical Institute of Chemistry CAS
Priority to CN201010263949.2A priority Critical patent/CN101935072B/en
Publication of CN101935072A publication Critical patent/CN101935072A/en
Application granted granted Critical
Publication of CN101935072B publication Critical patent/CN101935072B/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 discloses ferrous lithium sulphate fluoride as cathode materials of lithium batteries as well as a preparation method and application thereof. The ferrous sulphate lithium fluoride is prepared according to the following steps of: adding FeSO4.xH2O, LiF and a solvent into a reaction container and mixing the added substances to obtain a reaction solution, and heating the reaction solution to 200-350 DEG C for reaction to obtain the ferrous sulphate fluoride, wherein x in the FeSO4.xH2O is an integer greater than or equal to 0, and the solvent is alcohol or polyethylene glycol containing at least one hydroxide radical. In the invention, the preparation method is simple and the raw materials are rich and easy to obtain; thus, the preparation method is suitable for mass production and has high practicality degree. In addition the obtained ferrous lithium sulphate fluoride is in nanoparticles with high actual capacity and can be directly used as cathode materials of lithium-ion batteries.

Description

Ferrous lithium of fluorosulfuric acid and preparation method thereof and application
Technical field
The present invention relates to ferrous lithium of a kind of fluorosulfuric acid and preparation method thereof and application.
Background technology
Along with the widespread use of lithium ion battery in portable type electronic product, electromobile and instant-plugging hybrid electric vehicle, to anode material for lithium-ion batteries (as LiCoO 2, LiMn 2O 4, LiFePO 4) and negative material (as C, Sn, research Si) is deep day by day.With respect to negative material, the research of positive electrode material then relatively lags behind.As business-like LiCoO 2There are problems such as stability, cost and environment.LiFePO 4Because of cheap, aboundresources and non-environmental-pollution problem, moderate voltage platform and higher advantages such as capacity become hot of research and development.But LiFePO 4Poorly conductive has limited making full use of of its active material, need carry out carbon to it and coat or doping vario-property.The novel LiMSO of report one class such as M.Armand in 2009 4F (M=3d metal) material, the wherein ferrous lithium (LiFeSO of fluorosulfuric acid 4F) present excellent chemical property.LiFeSO 4The charge and discharge platform 3.6V of F is a little more than LiFePO 4Charge and discharge platform, theoretical capacity 151mAh/g is a little less than LiFePO 4But LiFeSO 4The ion of F and electronic conduction performance are better than LiFePO 4, help improving the performance of lithium ion battery.Therefore, LiFeSO 4F is considered to the new type lithium ion battery positive electrode material that the utmost point has application potential.But need to adopt ionic liquid as solvent in the preparation process of having reported, severe reaction conditions to having relatively high expectations of equipment, is unfavorable for scale operation, has limited its competitive edge and application widely.
Summary of the invention
The purpose of this invention is to provide ferrous lithium of a kind of anode material for lithium-ion batteries fluorosulfuric acid and preparation method thereof.
The ferrous lithium of fluorosulfuric acid provided by the present invention is to prepare according to the method that comprises the steps: add FeSO in reaction vessel 4XH 2O, LiF and solvent mix, and get reaction soln; Again described reaction soln is heated to 200-350 ℃ and reacts, it is ferrous to obtain described fluorosulfuric acid; Wherein, described FeSO 4XH 2X among the O is the integer more than or equal to 0, and described solvent is alcohol or the polyoxyethylene glycol that contains at least one hydroxyl.
Among the present invention, described FeSO 4XH 2O specifically can be following any one: FeSO 4, FeSO 4H 2O, FeSO 44H 2O and FeSO 47H 2O.
The described alcohol that contains at least one hydroxyl is triacontanol price quote, benzhydrol, and glycerol or Tetraglycol 99 are preferably benzhydrol, glycerol or Tetraglycol 99.
The weight-average molecular weight of described polyoxyethylene glycol can be 200-20000, is preferably 200-1000.
FeSO in the described reaction soln 4XH 2The mol ratio of O and LiF can be 1: 1-1.5 is preferably 1: 1-1.2.
The reaction times of described reaction can be 1-72h, preferred 5-60h.
The prepared ferrous lithium of fluorosulfuric acid of the present invention exists with the ferrous lithium particulate of fluorosulfuric acid form, and the ferrous lithium particle grain size of described fluorosulfuric acid can be 10nm-2 μ m.
Further object of the present invention provides the application of the ferrous lithium of described fluorosulfuric acid.
Application provided by the present invention is the application of the ferrous lithium of fluorosulfuric acid as battery electrode material, particularly as the application of anode material for lithium-ion batteries.
The present invention also provides a kind of energy storage elements, and described energy storage elements contains the ferrous lithium of described fluorosulfuric acid, this energy storage elements preferred lithium ionization cell.
The present invention also provides a kind of portable electric appts, and this electronics uses above-mentioned energy storage elements, the preferred mobile telephone of this portable electric appts, photographic camera, pick up camera, MP3, MP4, notebook computer.
Compared with prior art, the method for preparing the ferrous lithium of fluorosulfuric acid provided by the invention is simple, and raw material is easy to get, suitable for mass production, degree of being practical height.And the ferrous lithium of the fluorosulfuric acid that obtains is a nano material, can be directly uses as the electrode materials of battery.
Description of drawings
Fig. 1 is X-ray diffraction (XRD) figure of the ferrous lithium of fluorosulfuric acid of embodiment 1 preparation.
Fig. 2 is the ferrous lithium electron scanning micrograph of fluorosulfuric acid of embodiment 1 preparation.
Fig. 3 is the charging and discharging curve when the ferrous lithium of fluorosulfuric acid is as anode material for lithium-ion batteries among the embodiment 1.
Embodiment
The invention will be further described below in conjunction with specific embodiment, but the present invention is not limited to following examples.
Experimental technique described in the following embodiment if no special instructions, is ordinary method; Described reagent and material all can obtain from commercial channels.
Embodiment 1, the ferrous lithium of preparation fluorosulfuric acid
Press FeSO 4H 2O: LiF=1: 1.1 mol ratio takes by weighing, and adds Tetraglycol 99 as solvent, mixes.React 5h down at 300 ℃.Reaction finishes, and separates drying, obtains pulverulent solids.
With powder x-ray diffraction (Rigaku DmaxrB, CuK αRay) analyzes the conclusive evidence structure.The result as shown in Figure 1.As can be seen from the figure, there is not impurity peaks in the spectrogram, the product purity height is described.
Characterized the pattern of the ferrous lithium of fluorosulfuric acid with scanning electronic microscope (JEOL-6700F), as shown in Figure 2.As seen from the figure, the grain diameter scope of this material is 20-200nm, is that particle and the particle diameter of 159.4nm is the particle of 71.7nm as the particle diameter that indicates among the figure.
The chemical property of the ferrous lithium of fluorosulfuric acid characterizes:
The ferrous lithium of the fluorosulfuric acid for preparing, carbon black and binding agent are made into slurry with mass ratio mixing in 70: 20: 10, be coated to equably and obtain working electrode on the aluminum foil current collector, as counter electrode, glass fibre membrane (Britain Whatman company) is as barrier film with the lithium sheet metal, 1mol/L LiPF 6(solvent is 1: 1 NSC 11801 of volume ratio and methylcarbonate mixed solution) as electrolytic solution, assembling obtains Swagelok type battery in glove box.
The battery of above-mentioned assembling is carried out charge-discharge test on LAND charge-discharge test instrument, the interval that discharges and recharges of test is 4.2-2.5V.
The result as shown in Figure 3, the ferrous lithium of synthetic fluorosulfuric acid has good charging and discharging curve.As seen, when the ferrous lithium of synthetic fluorosulfuric acid of the present invention is used as anode material for lithium-ion batteries, has chemical property.Ferrous lithium of the fluorosulfuric acid for preparing in the present embodiment and simulated battery test result are listed in table 1.
Embodiment 2, the ferrous lithium of preparation fluorosulfuric acid
Press FeSO 4H 2O: LiF=1: 1.15 mol ratio takes by weighing, and adds glycerol as solvent, mixes.React 36h down at 285 ℃.Finish, separate drying, obtain pulverulent solids.Ferrous lithium of the fluorosulfuric acid for preparing in the present embodiment and simulated battery test result are listed in table 1.
Embodiment 3, the ferrous lithium of preparation fluorosulfuric acid
Press FeSO 4H 2O: LiF=1: 1.2 mol ratio takes by weighing, and adds polyoxyethylene glycol (weight-average molecular weight is 200) and as solvent, mixes.React 60h down at 250 ℃.Finish, separate drying, obtain pulverulent solids.Ferrous lithium of the fluorosulfuric acid for preparing in the present embodiment and simulated battery test result are listed in table 1.
Embodiment 4, the ferrous lithium of preparation fluorosulfuric acid
Press FeSO 4H 2O: LiF=1: 1.2 mol ratio takes by weighing, and adds polyoxyethylene glycol (weight-average molecular weight is 300) and as solvent, mixes.React 12h down at 310 ℃.Finish, separate drying, obtain pulverulent solids.Ferrous lithium of the fluorosulfuric acid for preparing in the present embodiment and simulated battery test result are listed in table 1.
Embodiment 5, the ferrous lithium of preparation fluorosulfuric acid
Press FeSO 4H 2O: LiF=1: 1.15 mol ratio takes by weighing, and adds polyoxyethylene glycol (weight-average molecular weight is 400) and as solvent, mixes.React 2h down at 340 ℃.Finish, separate drying, obtain pulverulent solids.Ferrous lithium of the fluorosulfuric acid for preparing in the present embodiment and simulated battery test result are listed in table 1.
Embodiment 6, the ferrous lithium of preparation fluorosulfuric acid
Press FeSO 44H 2O: LiF=1: 1.05 mol ratio takes by weighing, and adds Tetraglycol 99 as solvent, mixes.React 24h down at 320 ℃.Finish, separate drying, obtain pulverulent solids.Ferrous lithium of the fluorosulfuric acid for preparing in the present embodiment and simulated battery test result are listed in table 1.
Embodiment 7, the ferrous lithium of preparation fluorosulfuric acid
Press FeSO 44H 2O: LiF=1: 1 mol ratio takes by weighing, and adds glycerol as solvent, mixes.React 60h down at 285 ℃.Finish, separate drying, obtain pulverulent solids.Ferrous lithium of the fluorosulfuric acid for preparing in the present embodiment and simulated battery test result are listed in table 1.
Embodiment 8, the ferrous lithium of preparation fluorosulfuric acid
Press FeSO 44H 2O: LiF=1: 1.3 mol ratio takes by weighing, and adds polyoxyethylene glycol (weight-average molecular weight is 200) and as solvent, mixes.React 72h down at 220 ℃.Finish, separate drying, obtain pulverulent solids.Ferrous lithium of the fluorosulfuric acid for preparing in the present embodiment and simulated battery test result are listed in table 1.
Embodiment 9, the ferrous lithium of preparation fluorosulfuric acid
Press FeSO 44H 2O: LiF=1: 1.2 mol ratio takes by weighing, and adds polyoxyethylene glycol (weight-average molecular weight is 300) and as solvent, mixes.React 36h down at 280 ℃.Finish, separate drying, obtain pulverulent solids.Ferrous lithium of the fluorosulfuric acid for preparing in the present embodiment and simulated battery test result are listed in table 1.
Embodiment 10, the ferrous lithium of preparation fluorosulfuric acid
Press FeSO 44H 2O LiF=1: 1.1 mol ratio takes by weighing, and adds polyoxyethylene glycol (weight-average molecular weight is 20000) and as solvent, mixes.React 8h down at 320 ℃.Finish, separate drying, obtain pulverulent solids.Ferrous lithium of the fluorosulfuric acid for preparing in the present embodiment and simulated battery test result are listed in table 1.
Embodiment 11, the ferrous lithium of preparation fluorosulfuric acid
Press FeSO 47H 2O: LiF=1: 1.15 mol ratio takes by weighing, and adds Tetraglycol 99 as solvent, mixes.React 12h down at 325 ℃.Finish, separate drying, obtain pulverulent solids.Ferrous lithium of the fluorosulfuric acid for preparing in the present embodiment and simulated battery test result are listed in table 1.
Embodiment 12, the ferrous lithium of preparation fluorosulfuric acid
Press FeSO 47H 2O: LiF=1: 1.5 mol ratio takes by weighing, and adds glycerol as solvent, mixes.React 48h down at 290 ℃.Finish, separate drying, obtain pulverulent solids.Ferrous lithium of the fluorosulfuric acid for preparing in the present embodiment and simulated battery test result are listed in table 1.
Embodiment 13, the ferrous lithium of preparation fluorosulfuric acid
Press FeSO 47H 2O: LiF=1: 1.2 mol ratio takes by weighing, and adds polyoxyethylene glycol (weight-average molecular weight is 200) and as solvent, mixes.React 72h down at 285 ℃.Finish, separate drying, obtain pulverulent solids.Ferrous lithium of the fluorosulfuric acid for preparing in the present embodiment and simulated battery test result are listed in table 1.
Embodiment 14, the ferrous lithium of preparation fluorosulfuric acid
Press FeSO 47H 2O: LiF=1: 1.5 mol ratio takes by weighing, and adds polyoxyethylene glycol (weight-average molecular weight is 300) and as solvent, mixes.React 12h down at 310 ℃.Finish, separate drying, obtain pulverulent solids.Ferrous lithium of the fluorosulfuric acid for preparing in the present embodiment and simulated battery test result are listed in table 1.
Embodiment 15, the ferrous lithium of preparation fluorosulfuric acid
Press FeSO 47H 2O: LiF=1: 1.15 mol ratio takes by weighing, and adds polyoxyethylene glycol (weight-average molecular weight is 400) and as solvent, mixes.React 10h down at 300 ℃.Finish, separate drying, obtain pulverulent solids.Ferrous lithium of the fluorosulfuric acid for preparing in the present embodiment and simulated battery test result are listed in table 1.
Embodiment 16, the ferrous lithium of preparation fluorosulfuric acid
Press FeSO 4: LiF=1: 1.3 mol ratio takes by weighing, and adds polyoxyethylene glycol (weight-average molecular weight is 400) and as solvent, mixes.React 18h down at 300 ℃.Finish, separate drying, obtain pulverulent solids.Ferrous lithium of the fluorosulfuric acid for preparing in the present embodiment and simulated battery test result are listed in table 1.
Embodiment 17, the ferrous lithium of preparation fluorosulfuric acid
Press FeSO 44H 2O: LiF=1: 1.2 mol ratio takes by weighing, and adds polyoxyethylene glycol (weight-average molecular weight is 1000) and as solvent, mixes.React 8h down at 320 ℃.Finish, separate drying, obtain pulverulent solids.Ferrous lithium of the fluorosulfuric acid for preparing in the present embodiment and simulated battery test result are listed in table 1.
Embodiment 18, the ferrous lithium of preparation fluorosulfuric acid
Press FeSO 4H 2O: LiF=1: 1.15 mol ratio takes by weighing, and adds benzhydrol as solvent, mixes.React 10h down at 298 ℃.Finish, separate drying, obtain pulverulent solids.Ferrous lithium of the fluorosulfuric acid for preparing in the present embodiment and simulated battery test result are listed in table 1.
The preparation condition of table 1, the ferrous lithium material of fluorosulfuric acid and simulated battery test result
Figure BSA00000247713800061
According to the result of table 1 as can be seen, the present invention is a reaction media with alcohol or the polyoxyethylene glycol that contains at least one hydroxyl, utilizes FeSO 4XH 2O is that source of iron and LiF can conveniently prepare the ferrous lithium anode material of fluorosulfuric acid for the lithium source.Utilize the inventive method not only can reduce the preparation cost of material greatly, and the ferrous lithium anode material of fluorosulfuric acid that the present invention obtains has all shown higher capacity.

Claims (10)

1. a method for preparing the ferrous lithium of fluorosulfuric acid comprises the steps: to add FeSO in reaction vessel 4XH 2O, LiF and solvent mix, and get reaction soln; Again described reaction soln is heated to 200-350 ℃ and reacts, it is ferrous to obtain described fluorosulfuric acid; Wherein, described FeSO 4XH 2X among the O is the integer more than or equal to 0, and described solvent is alcohol or the polyoxyethylene glycol that contains at least one hydroxyl.
2. method according to claim 1 is characterized in that: described FeSO 4XH 2O be following any one: FeSO 4, FeSO 4H 2O, FeSO 44H 2O and FeSO 47H 2O.
3. method according to claim 1 and 2 is characterized in that: the described alcohol that contains at least one hydroxyl is triacontanol price quote, benzhydrol, and glycerol or Tetraglycol 99 are preferably benzhydrol, glycerol or Tetraglycol 99; The weight-average molecular weight of described polyoxyethylene glycol is 200-20000, is preferably 200-1000.
4. according to arbitrary described method among the claim 1-3, it is characterized in that: FeSO in the described reaction soln 4XH 2The mol ratio of O and LiF is 1: 1-1.5 is preferably 1: 1-1.2.
5. according to arbitrary described method among the claim 1-4, it is characterized in that: the reaction times of described reaction is 1-72h, preferred 5-60h.
6. the ferrous lithium of fluorosulfuric acid that arbitrary described method prepares among the claim 1-5.
7. the ferrous lithium of fluorosulfuric acid according to claim 6 is characterized in that: the ferrous lithium of described fluorosulfuric acid exists with the ferrous lithium particulate of fluorosulfuric acid form, and the ferrous lithium particle grain size of described fluorosulfuric acid is 10nm-2 μ m.
8. claim 6 or the ferrous lithium of 7 described fluorosulfuric acids are as the application of battery electrode material, and described battery electrode material is preferably anode material for lithium-ion batteries.
9. energy storage elements, it is characterized in that: described energy storage elements contains claim 6 or the ferrous lithium of 7 described fluorosulfuric acids.
10. a portable electric appts is characterized in that: the energy storage elements that described portable electric appts uses claim 9 to state.
CN201010263949.2A 2010-08-26 2010-08-26 Ferrous lithium sulphate fluoride as well as preparation method and application thereof Active CN101935072B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201010263949.2A CN101935072B (en) 2010-08-26 2010-08-26 Ferrous lithium sulphate fluoride as well as preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201010263949.2A CN101935072B (en) 2010-08-26 2010-08-26 Ferrous lithium sulphate fluoride as well as preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN101935072A true CN101935072A (en) 2011-01-05
CN101935072B CN101935072B (en) 2014-01-29

Family

ID=43388680

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201010263949.2A Active CN101935072B (en) 2010-08-26 2010-08-26 Ferrous lithium sulphate fluoride as well as preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN101935072B (en)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102332580A (en) * 2011-03-15 2012-01-25 中国科学院物理研究所 Fluorinated ferric sulfate salt compound as well as preparation method and application thereof
CN103178244A (en) * 2011-12-23 2013-06-26 财团法人工业技术研究院 Hybrid energy storage element
CN105668643A (en) * 2016-01-11 2016-06-15 华南师范大学 Method for preparing lithium ion batteries cathode material
CN106853997A (en) * 2016-12-14 2017-06-16 北京理工大学 A kind of positive electrode and preparation method thereof and positive pole coating material and lithium ion battery
CN106876793A (en) * 2017-03-15 2017-06-20 山东威林特新能源科技有限公司 A kind of lithium titanate battery preparation method of high circulation performance
CN106920965A (en) * 2017-05-10 2017-07-04 江西理工大学 A kind of new sodium ion positive electrode NaFeSO4The preparation method of F
CN108054360A (en) * 2017-12-08 2018-05-18 安徽天时新能源科技有限公司 A kind of low temperature lithium battery fluorination ferric sulfate lithium anode material and preparation method thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101007630A (en) * 2007-01-16 2007-08-01 北大先行科技产业有限公司 Particle appearance regulatory lithium iron phosphate preparation method
CN101330141A (en) * 2008-07-18 2008-12-24 清华大学 Method for preparing lithium ionic battery anode material spherical LiFePO4 /C

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101007630A (en) * 2007-01-16 2007-08-01 北大先行科技产业有限公司 Particle appearance regulatory lithium iron phosphate preparation method
CN101330141A (en) * 2008-07-18 2008-12-24 清华大学 Method for preparing lithium ionic battery anode material spherical LiFePO4 /C

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
《NATURE MATERIALS》 20091129 N. Recham et al. A 3.6V lithium-based fluorosulphate insertion positive electrode for lithium-ion batteries 第68-74页 1-10 第9卷, 2 *

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102332580A (en) * 2011-03-15 2012-01-25 中国科学院物理研究所 Fluorinated ferric sulfate salt compound as well as preparation method and application thereof
WO2012122686A1 (en) * 2011-03-15 2012-09-20 中国科学院物理研究所 Fluorinated lithium iron sulfate compound, preparation method and use thereof
CN102332580B (en) * 2011-03-15 2013-11-27 中国科学院物理研究所 Fluorinated ferric sulfate salt compound as well as preparation method and application thereof
CN103178244A (en) * 2011-12-23 2013-06-26 财团法人工业技术研究院 Hybrid energy storage element
CN103178244B (en) * 2011-12-23 2016-03-16 财团法人工业技术研究院 Hybrid energy storage element
CN105668643A (en) * 2016-01-11 2016-06-15 华南师范大学 Method for preparing lithium ion batteries cathode material
CN106853997A (en) * 2016-12-14 2017-06-16 北京理工大学 A kind of positive electrode and preparation method thereof and positive pole coating material and lithium ion battery
CN106876793A (en) * 2017-03-15 2017-06-20 山东威林特新能源科技有限公司 A kind of lithium titanate battery preparation method of high circulation performance
CN106920965A (en) * 2017-05-10 2017-07-04 江西理工大学 A kind of new sodium ion positive electrode NaFeSO4The preparation method of F
CN108054360A (en) * 2017-12-08 2018-05-18 安徽天时新能源科技有限公司 A kind of low temperature lithium battery fluorination ferric sulfate lithium anode material and preparation method thereof
CN108054360B (en) * 2017-12-08 2020-04-10 安徽天时新能源科技有限公司 Fluorinated lithium iron sulfate cathode material for low-temperature lithium battery and preparation method thereof

Also Published As

Publication number Publication date
CN101935072B (en) 2014-01-29

Similar Documents

Publication Publication Date Title
Liu et al. Exploring competitive features of stationary sodium ion batteries for electrochemical energy storage
CN107369825B (en) Nitrogen-doped carbon-coated manganese oxide lithium ion battery composite negative electrode material and preparation method and application thereof
Barghamadi et al. A review on Li-S batteries as a high efficiency rechargeable lithium battery
CN100461507C (en) Making method for nano LiFePO4-carbon composite cathode material
CN101935072B (en) Ferrous lithium sulphate fluoride as well as preparation method and application thereof
Cheng et al. A macaroni-like Li1. 2V3O8 nanomaterial with high capacity for aqueous rechargeable lithium batteries
CN106058168A (en) Prelithiated positive electrode material for lithium ion secondary battery
CN102244233B (en) Method for preparing composite cathode material of graphene-like doped-cladded lithium titanate
CN102820456B (en) Porous carbon/sulfur composite material, its preparation method and application
CN109671946B (en) Zinc ion battery positive electrode active material, positive electrode material, zinc ion battery positive electrode, zinc ion battery, and preparation method and application thereof
KR101684645B1 (en) A nano-composite of V2O5 xerogel and carbon, and cathode for rechargeable lithium sulfur battery comprising the same, and preparation process thereof
CN102290572A (en) Cathode active substance and cathode used for lithiumion secondary battery
CN101931073B (en) Preparation method of lithium iron phosphate/carbon composite cathode material
CN106935830B (en) lithium ion battery composite positive electrode material and preparation method and application thereof
Huang et al. Al3+-doped FeNb11O29 anode materials with enhanced lithium-storage performance
Li et al. Formation of Mn–Ni prussian blue analogue spheres as a superior cathode material for potassium-ion batteries
CN102751489B (en) Method for preparing anode material of lithium ion battery
Wu et al. Sodium-based dual-ion battery based on the organic anode and ionic liquid electrolyte
CN100374366C (en) Process for solid phase synthesis of lithium iron phosphate anode materials under high pressure
CN103367735B (en) A kind of magnesium secondary battery anode material and application thereof
CN111129491A (en) Lithium ion battery negative electrode active material, preparation method thereof and lithium ion battery
CN107910528B (en) Lithium titanate composite material, preparation method thereof, negative plate and lithium ion battery
CN101774563A (en) High-voltage positive electrode material used by lithium ion battery and preparation method thereof
CN104009215A (en) Vanadium dioxide-graphene compound and its use as lithium ion battery positive electrode material
Xing et al. CeO2/Ce2S3 modified carbon nanotubes as efficient cathode materials for lithium-sulfur batteries

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