CN104591296A - High-performance hybrid crystal system ferric fluoride positive electrode material and preparation method thereof - Google Patents

High-performance hybrid crystal system ferric fluoride positive electrode material and preparation method thereof Download PDF

Info

Publication number
CN104591296A
CN104591296A CN201410846347.8A CN201410846347A CN104591296A CN 104591296 A CN104591296 A CN 104591296A CN 201410846347 A CN201410846347 A CN 201410846347A CN 104591296 A CN104591296 A CN 104591296A
Authority
CN
China
Prior art keywords
preparation
anode material
water
ferric fluoride
crystallographic system
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
CN201410846347.8A
Other languages
Chinese (zh)
Other versions
CN104591296B (en
Inventor
乔文灿
宋春华
王胜伟
王瑛
王文阁
赵成龙
陈欣
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.)
Shandong Yuhuang Chemical Co Ltd
Shandong Yuhuang New Energy Technology Co Ltd
Original Assignee
Shandong Yuhuang Chemical Co Ltd
Shandong Yuhuang New Energy Technology Co Ltd
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 Shandong Yuhuang Chemical Co Ltd, Shandong Yuhuang New Energy Technology Co Ltd filed Critical Shandong Yuhuang Chemical Co Ltd
Priority to CN201410846347.8A priority Critical patent/CN104591296B/en
Publication of CN104591296A publication Critical patent/CN104591296A/en
Application granted granted Critical
Publication of CN104591296B publication Critical patent/CN104591296B/en
Active 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 in particular relates to a high-performance hybrid crystal system ferric fluoride positive electrode material and a preparation method thereof. The positive electrode material is prepared from a water/alcohol mixed solution containing a ferric salt and a fluorine-containing water/alcohol mixed solution. The preparation method is performed under normal temperature and normal pressure, the preparation process is simple, and the method is low in time consumption, low in energy consumption, low in cost, environment-friendly and easy for industrial production; and the prepared hybrid crystal system FeF3(H2O)0.33/beta-FeF3.3H2O nanoparticles have high specific discharge capacity, low cost, environment friendliness, high rate capability and excellent cycling stability and have actual application prospects in the fields of power supplies and battery energy storage.

Description

A kind of high-performance mixing crystallographic system ferric fluoride anode material and preparation method thereof
(1) technical field
The present invention relates to a kind of lithium ion secondary battery anode material, be specifically related to a kind of high-performance mixing crystallographic system ferric fluoride anode material and preparation method thereof.
(2) background technology
Lithium-ion secondary cell compares conventional lead acid, nickel metal hydride battery, has that quality is light, environmental protection, the life-span is long, capacity is large and security advantages of higher.Establish unrivaled dominant advantage in portable type electronic product fields such as mobile phone, notebook computer, digital cameras, and actively develop to power tool, electromobile, UPS equipment and national defence.
The development of high performance lithium ion battery depends on the technical progress of positive electrode material, and it directly affects the key property such as capacity, life-span, cost, security of battery.The development of development of new positive electrode material to new-energy automobile power battery and power energy storage field is significant.Because the electronegativity of fluorine is large, the operating voltage of metal fluoride positive electrode material is far above other positive electrode materials such as metal oxide, metallic sulfide.This reversible chemical conversioning reaction can make full use of the various oxidation state of material in redox processes, electronics all in exchange material, and its capacity of releasing is far away higher than the Lithium-ion embeding on traditional outline/deintercalation reaction.Equal within 1997, to propose transition metal fluorides as after the positive electrode material of lithium-ion secondary cell from Kyoto Univ Japan Arai, on U.S. MRS autumn sessions in 2002 and first international energy Conversion Project meeting in 2003, professor Amatucci again proposes metal fluoride and is used as lithium ion secondary battery anode material, has again caused the upsurge of metal fluoride positive electrode material research.FeF 3because it has high, with low cost, the eco-friendly advantage of specific storage, be considered to the anode material for lithium-ion batteries of new generation having researching value and application prospect.
FeF prepared by domestic and international research 3material is mostly R-3C spacer, belongs to ReO 3crystal formation, hexagonal system structure, its shortcoming is that conductivity is poor, and specific discharge capacity is low, and cycle performance is poor.At present mainly by FeF 3improve its conductivity with electro-conductive material (as graphite, carbon black, gac etc.) mixing and ball milling.AmatucciG.G etc. are by the nanometer Fe F of preparation carbon coated 3/ C composite improves FeF 3conductivity, but its cycle performance still can not get improve.Badway F etc. has prepared FeF by the method for high-energy ball milling 3base nano-sized carbon metal composite, in the voltage range of 2.8-3.4V, its capacity is up to 200mAh/g.Korea S Kang teach problem group adopts liquid phase method at the upper growth in situ FeF of carbon nanotube (CNT) 3nanometer flowers, obtain CNT-FeF 3nano composite material, this material within the scope of 2.0-4.5V, with 20mA/g discharge and recharge, first discharge specific capacity is up to 210mAh/g, and material circulation better performances but its cycle index is less, only has 30 weeks and material cost is higher, complicated process of preparation, the more difficult control of grain diameter growth.
In recent years, the FeF of rhombic system that had investigator to prepare 3(H 2o) 0.33material, a small amount of crystal water contributes to improving the chemical property of material the relatively stable of holding structure and obtaining good cycle performance.2011, Maier seminar for template introduces the Single Walled Carbon Nanotube (SWNT) of 5wt.% at low temperatures, formed SWNT/FeF with BmimBF4 ionic liquid 30.33H 2o matrix material improves the electroconductibility of ferric fluoride material further, and make material obtain better chemical property, first discharge specific capacity is up to 220mAh/g, but cycle performance is poor, and the capability retention after 50 times that circulates is 66%.
FeF 3the key of application solves its technology of preparing complexity and a difficult problem for the harsh length consuming time of condition, and improve its chemical property (electroconductibility, cyclicity and specific discharge capacity).At present, FeF 3preparation be obtained by anhydrous hydrofluoric acid or fluorine and ferric chloride reaction, or ferric oxide at high temperature reacts obtained with hydrogen fluoride gas.And improve electroconductibility also mainly by improving its conductivity with electro-conductive material (as graphite, carbon black, gac etc.) mixing and ball milling, fail its chemical property of radical change from structure and pattern.The positive electrode material homogeneity of such preparation is poor, time consumption and energy consumption, and environmental pollution is large, and the higher and complex process of product pattern noncontrollable cost, is not used in suitability for industrialized production.Rhombic system FeF 3(H 2o) 0.33with β-FeF 33H 2minor amount of water in O contributes to the electroconductibility improving material, and can improve FeF in charge and discharge process 3structural stability, and then improve cyclical stability.Reduce the raising that this material particle size size is conducive to high rate performance simultaneously, and adopt suitable reaction solvent system and add the size that effective tensio-active agent effectively can control material particle size, obtain nano structural material.Therefore have that heavy body, high rate performance and cyclical stability are excellent by the synthesis of optimization experiment method and to be applicable to the development of high-performance mixing crystallographic system ferric fluoride anode material to new-energy automobile power battery and power energy storage field of heavy industrialization significant.
(3) summary of the invention
The object of the invention is the FeF for hexagonal system structure 3there is the problem that preparation process condition complexity is harsh, energy consumption is high, chemical property is poor in positive electrode material, mixed crystal series high-performance ferric fluoride anode material providing a kind of rhombic system and tetragonal system and preparation method thereof.
The present invention is achieved through the following technical solutions:
A kind of high-performance mixing crystallographic system ferric fluoride anode material, its special character is: be prepared from by the water/mixed alkoxide solution and fluorine-containing water/mixed alkoxide solution that contain molysite.
A preparation method for high-performance mixing crystallographic system ferric fluoride anode material described in basis, comprises the following steps:
(1) at normal temperatures, water/the mixed alkoxide solution of preparation molysite, iron salt concentration is 0.5 ~ 0.6mol/L, add oleic acid wherein again, prepare by the mol ratio 1:3 of iron ion and fluorion water/mixed alkoxide solution that fluoro-containing concentration is 1mol/L, the ratio of wherein added water volume and the volume of alcohol is for being less than 1;
(2) by two kinds of solution described in step (1), add dispersion agent respectively, two kinds of solution are ultrasonic respectively;
(3) at the uniform velocity stir after again two kinds of solution being mixed at normal temperatures and pressures;
(4) fully centrifugation after reaction, outwells supernatant liquor, and with dehydrated alcohol repeatedly washing precipitate;
(5) throw out after washing is dry at 60-80 DEG C, obtain powdered sample FeF 3(H 2o) 0.33/ β-FeF 33H 2o.
The preparation method of high-performance mixing crystallographic system ferric fluoride anode material of the present invention, described molysite is Fe (NO 3) 39H 2o, FeCl 36H 2one in O.
The preparation method of high-performance mixing crystallographic system ferric fluoride anode material of the present invention, described alcohol is the one in ethanol, ethylene glycol.
The preparation method of high-performance mixing crystallographic system ferric fluoride anode material of the present invention, described fluorine-containing material is the one in Neutral ammonium fluoride, ammonium bifluoride.
The preparation method of high-performance mixing crystallographic system ferric fluoride anode material of the present invention, described dispersion agent is polyoxyethylene glycol, and its molecular weight is 20000.
The preparation method of high-performance mixing crystallographic system ferric fluoride anode material of the present invention, the addition of oleic acid is 0.02 ~ 0.025mol, and the addition of dispersion agent is 0.01 ~ 0.02g.
The preparation method of high-performance mixing crystallographic system ferric fluoride anode material of the present invention, in step (2), ultrasonic 10-30min, in step (3), stirs 2-4h, in step (5), dry 8-12h.
Beneficial effect: this preparation method carries out at normal temperatures and pressures, preparation technology is simple, and consuming time short, and energy consumption is low, with low cost, and environmental friendliness is easy to suitability for industrialized production; The mixing crystallographic system FeF of preparation 3(H 2o) 0.33/ β-FeF 33H 2o nano particle has higher specific discharge capacity, cost is low, environmental friendliness, high rate performance and cyclical stability excellent, has actual application prospect in electrical source of power and battery energy storage field.
(4) accompanying drawing explanation
The mixing crystallographic system positive electrode material FeF that figure mono-is prepared for the present invention 3(H 2o) 0.33/ β-FeF 33H 2o scanning electron microscope (SEM) photograph;
Figure bis-is the present invention's ratio of alcohol volume of water in reaction solvent is the mixing crystallographic system positive electrode material FeF prepared under 2:1,3:1 condition 3(H 2o) 0.33/ β-FeF 33H 2the X-ray diffraction spectrogram of O;
The mixing crystallographic system FeF that figure tri-is prepared for the present invention 3(H 2o) 0.33/ β-FeF 33H 2o is positive electrode material, and lithium sheet is negative material, is assembled into button cell, at room temperature with 0.5C, 1C and 2.0C multiplying power, and the cycle life curve in the voltage range of 2.0-4.5V.
(5) embodiment
Embodiment 1:
Preparing 40 mL concentration is 0.5 mol/L iron nitrate (Fe (NO 3) 39H 2o) water/alcohol mixed solution (volume ratio of ethanol and water is 2:1), and add 0.02mol oleic acid wherein; 1:3 prepares water/ethanolic soln (volume ratio of ethanol and water is 2:1) that 20 mL concentration are 1mol/L Neutral ammonium fluoride in molar ratio, then two kinds of solution are added 0.01g polyoxyethylene glycol (molecular weight 20000) respectively, two kinds of solution ultrasonic 30min respectively, again by two kinds of solution mixing, under normal temperature and pressure, at the uniform velocity stir 2 h.Centrifugally outwell supernatant liquor, and with ethanol repetitive scrubbing throw out repeatedly, after 60 DEG C of dry 8h, obtain target product FeF 3(H 2o) 0.33/ β-FeF 33H 2o.
Embodiment 2:
Preparing 40 mL concentration is respectively 0.6 mol/L iron(ic) chloride (FeCl 36H 2o) water/ethanolic soln (volume ratio of ethanol and water is 3:1), and add 0.025mol oleic acid wherein; 1:3 prepares water/ethanolic soln (volume ratio of ethanol and water is 3:1) that 24mL concentration is 1mol/L ammonium bifluoride in molar ratio, then two kinds of solution are added 0.02g polyoxyethylene glycol (molecular weight 20000) respectively, two kinds of solution ultrasonic 30min respectively, again by two kinds of solution mixing, under normal temperature and pressure, at the uniform velocity stir 4 h.Centrifugally outwell supernatant liquor, and with ethanol repetitive scrubbing throw out repeatedly, after 60 DEG C of dry 12h target product FeF 3(H 2o) 0.33/ β-FeF 33H 2o.
Embodiment 3:
Preparing 40 mL concentration is 0.5 mol/L iron nitrate (Fe (NO 3) 39H 2o) water/ethylene glycol mixing solutions (volume ratio of ethylene glycol and water is 3:1), and add 0.025mol oleic acid wherein; 1:3 prepares water/ethylene glycol mixing solutions (volume ratio of ethylene glycol and water is 3:1) that 20 mL concentration are 1mol/L Neutral ammonium fluoride in molar ratio, then two kinds of solution are added 0.01g polyoxyethylene glycol (molecular weight 20000) respectively, two kinds of solution ultrasonic 30min respectively, again by two kinds of solution mixing, under normal temperature and pressure, at the uniform velocity stir 2 h.Centrifugally outwell supernatant liquor, and with ethanol repetitive scrubbing throw out repeatedly, after 60 DEG C of dry 8h, obtain target product FeF 3(H 2o) 0.33/ β-FeF 33H 2o.
Embodiment 4:
Preparing 40 mL concentration is respectively 0.6 mol/L iron(ic) chloride (FeCl 36H 2o) water/ethylene glycol solution (volume ratio of ethylene glycol and water is 2:1), and add 0.025mol oleic acid wherein; 1:3 prepares water/ethylene glycol solution (volume ratio of ethylene glycol and water is 2:1) that 24mL concentration is 1mol/L ammonium bifluoride in molar ratio, then two kinds of solution are added 0.02g polyoxyethylene glycol (molecular weight 20000) respectively, two kinds of solution ultrasonic 30min respectively, again by two kinds of solution mixing, under normal temperature and pressure, at the uniform velocity stir 4 h.Centrifugally outwell supernatant liquor, and with ethanol repetitive scrubbing throw out repeatedly, after 60 DEG C of dry 12h, obtain target product FeF 3(H 2o) 0.33/ β-FeF 33H 2o.
Embodiment 5:
Preparing 40 mL concentration is respectively 0.6 mol/L iron(ic) chloride (FeCl 36H 2o) water/ethylene glycol solution (volume ratio of ethylene glycol and water is 2:1), and add 0.022mol oleic acid wherein; 1:3 prepares water/ethylene glycol solution (volume ratio of ethylene glycol and water is 2:1) that 24mL concentration is 1mol/L ammonium bifluoride in molar ratio, then two kinds of solution are added 0.015g polyoxyethylene glycol (molecular weight 20000) respectively, two kinds of solution ultrasonic 30min respectively, again by two kinds of solution mixing, under normal temperature and pressure, at the uniform velocity stir 3 h.Centrifugally outwell supernatant liquor, and with ethanol repetitive scrubbing throw out repeatedly, after 80 DEG C of dry 10h, obtain target product FeF 3(H 2o) 0.33/ β-FeF 33H 2o.
Embodiment 6:
Preparing 40 mL concentration is respectively 0.6 mol/L iron(ic) chloride (FeCl 36H 2o) water/ethylene glycol solution (volume ratio of ethylene glycol and water is 2:1), and add 0.4mol oleic acid, 0.005mol Dodecyl trimethyl ammonium chloride wherein; 1:3.5 prepares water/ethylene glycol solution (volume ratio of ethylene glycol and water is 2:1) that 24mL concentration is 1mol/L ammonium bifluoride in molar ratio, then two kinds of solution are added 0.015g polyoxyethylene glycol (molecular weight 20000) respectively, two kinds of solution ultrasonic 40min respectively, again by two kinds of solution mixing, under normal temperature and pressure, at the uniform velocity stir 0.4 h.Centrifugally outwell supernatant liquor, and with ethanol: ether be the mixed solution repetitive scrubbing throw out of 1:1.2 repeatedly, after 80 DEG C of dry 0.5h, obtain target product FeF 3(H 2o) 0.33/ β-FeF 33H 2o.
As shown in Figure 1, the FeF prepared by the present invention 3(H 2o) 0.33/ β-FeF 33H 2o particle is nanostructure, and particle dispersion is good.
As shown in Figure 2, the present invention's ratio of alcohol volume of water in reaction solvent system is the mixing crystallographic system FeF prepared under 2:1,3:1 condition 3(H 2o) 0.33/ β-FeF 33H 2the X-ray diffraction spectrogram of O, shows the content of often kind of crystallographic system in the ratio controllable mixing crystallographic system by changing reaction solvent water alcohol volume.
As shown in Figure 3, prepared mixing crystallographic system FeF 3(H 2o) 0.33/ β-FeF 33H 2o is as positive electrode material, and lithium is negative material, assembling button cell, at voltage window 2.0-4.5 V, and cycle life curve under 0.5C, 1C and 2C multiplying power.FeF 3(H 2o) 0.33discharge and recharge under 0.5C, first discharge specific capacity reaches 213.6 mAh/g, and close to theoretical capacity 237 mAh/g, after circulating 100 weeks, its specific discharge capacity is 165.3mAh/g; Under 1C, its first all specific discharge capacity of discharge and recharge still can reach 189.5 mAh/g, and after circulating 100 weeks, its capacity still can reach 143.3 mAh/g; Even if its first all specific discharge capacity of discharge and recharge still can reach 167.4 mAh/g under high magnification 2C, after circulating 100 weeks, its capacity still can reach 137.1 mAh/g, capability retention is 82.0%, and this positive electrode material has higher specific discharge capacity and high rate performance and cyclical stability excellence.

Claims (8)

1. a high-performance mixing crystallographic system ferric fluoride anode material, is characterized in that: be prepared from by the water/mixed alkoxide solution and fluorine-containing water/mixed alkoxide solution that contain molysite.
2. a preparation method for high-performance mixing crystallographic system ferric fluoride anode material according to claim 1, is characterized in that: comprise the following steps:
(1) at normal temperatures, water/the mixed alkoxide solution of preparation molysite, iron salt concentration is 0.5 ~ 0.6mol/L, add oleic acid wherein again, prepare by the mol ratio 1:3 of iron ion and fluorion water/mixed alkoxide solution that fluoro-containing concentration is 1mol/L, the ratio of wherein added water volume and the volume of alcohol is for being less than 1;
(2) by two kinds of solution described in step (1), add dispersion agent respectively, two kinds of solution are ultrasonic respectively;
(3) at the uniform velocity stir after again two kinds of solution being mixed at normal temperatures and pressures;
(4) fully centrifugation after reaction, outwells supernatant liquor, and with dehydrated alcohol repeatedly washing precipitate;
(5) throw out after washing is dry at 60-80 DEG C, obtain powdered sample FeF 3(H 2o) 0.33/ β-FeF 33H 2o.
3. the preparation method of high-performance mixing crystallographic system ferric fluoride anode material according to claim 2, is characterized in that: described molysite is Fe (NO 3) 39H 2o, FeCl 36H 2one in O.
4. the preparation method of the high-performance mixing crystallographic system ferric fluoride anode material according to Claims 2 or 3, is characterized in that: described alcohol is the one in ethanol, ethylene glycol.
5. the preparation method of the high-performance mixing crystallographic system ferric fluoride anode material according to Claims 2 or 3, is characterized in that: described fluorine-containing material is the one in Neutral ammonium fluoride, ammonium bifluoride.
6. the preparation method of the high-performance mixing crystallographic system ferric fluoride anode material according to Claims 2 or 3, it is characterized in that: described dispersion agent is polyoxyethylene glycol, its molecular weight is 20000.
7. the preparation method of the high-performance mixing crystallographic system ferric fluoride anode material according to Claims 2 or 3, it is characterized in that: the addition of oleic acid is 0.02 ~ 0.025mol, the addition of dispersion agent is 0.01 ~ 0.02g.
8. the preparation method of the high-performance mixing crystallographic system ferric fluoride anode material according to Claims 2 or 3, is characterized in that: in step (2), ultrasonic 10-30min, in step (3), stirs 2-4h, in step (5), and dry 8-12h.
CN201410846347.8A 2014-12-31 2014-12-31 A kind of high-performance mixing crystallographic system ferric fluoride anode material and preparation method thereof Active CN104591296B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201410846347.8A CN104591296B (en) 2014-12-31 2014-12-31 A kind of high-performance mixing crystallographic system ferric fluoride anode material and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201410846347.8A CN104591296B (en) 2014-12-31 2014-12-31 A kind of high-performance mixing crystallographic system ferric fluoride anode material and preparation method thereof

Publications (2)

Publication Number Publication Date
CN104591296A true CN104591296A (en) 2015-05-06
CN104591296B CN104591296B (en) 2016-09-14

Family

ID=53117413

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201410846347.8A Active CN104591296B (en) 2014-12-31 2014-12-31 A kind of high-performance mixing crystallographic system ferric fluoride anode material and preparation method thereof

Country Status (1)

Country Link
CN (1) CN104591296B (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110554078A (en) * 2019-09-27 2019-12-10 溧阳天目先导电池材料科技有限公司 Method for detecting LATP (LATP) of solid electrolyte lithium titanium aluminum phosphate
CN116111097A (en) * 2023-04-11 2023-05-12 宁德新能源科技有限公司 Conductive coating composition for electrode sheet, secondary battery, and electronic device

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103151522A (en) * 2013-02-28 2013-06-12 湘潭大学 Mixed crystal form ferric fluoride cathode material and preparation method thereof
CN103151523A (en) * 2013-02-28 2013-06-12 湘潭大学 Preparation method of cuboid-shaped positive-pole FeF3(H2O)0.33 material
JP2014043385A (en) * 2012-08-28 2014-03-13 Honda Motor Co Ltd MANUFACTURING METHOD OF FeF3

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014043385A (en) * 2012-08-28 2014-03-13 Honda Motor Co Ltd MANUFACTURING METHOD OF FeF3
CN103151522A (en) * 2013-02-28 2013-06-12 湘潭大学 Mixed crystal form ferric fluoride cathode material and preparation method thereof
CN103151523A (en) * 2013-02-28 2013-06-12 湘潭大学 Preparation method of cuboid-shaped positive-pole FeF3(H2O)0.33 material

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
ZHEN LONG等: "Mesoporous Iron Trifluoride Microspheres as Cathode Materials for Li-ion Batteries", 《ELECTROCHIMICA ACTA》, vol. 151, 7 November 2014 (2014-11-07), pages 355 - 362 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110554078A (en) * 2019-09-27 2019-12-10 溧阳天目先导电池材料科技有限公司 Method for detecting LATP (LATP) of solid electrolyte lithium titanium aluminum phosphate
CN110554078B (en) * 2019-09-27 2022-02-22 溧阳天目先导电池材料科技有限公司 Method for detecting LATP (LATP) of solid electrolyte lithium titanium aluminum phosphate
CN116111097A (en) * 2023-04-11 2023-05-12 宁德新能源科技有限公司 Conductive coating composition for electrode sheet, secondary battery, and electronic device

Also Published As

Publication number Publication date
CN104591296B (en) 2016-09-14

Similar Documents

Publication Publication Date Title
CN103151522B (en) A kind of ferric fluoride anode material preparation method mixing crystal formation
Zhang et al. Mesoporous Fe2O3 nanoparticles as high performance anode materials for lithium-ion batteries
CN103151523B (en) Preparation method of cuboid-shaped positive-pole FeF3(H2O)0.33 material
CN104993125B (en) A kind of lithium ion battery negative material Fe3O4The preparation method of/Ni/C
CN104966824A (en) Nitrogen-doped porous carbon sphere and cobaltous oxide nano-composite anode material based on chitosan and derivatives thereof and preparation method thereof
CN104183832B (en) A kind of preparation method of the FeF3 flexible electrodes based on CNT Graphene complex three-dimensional network and application
CN103326007B (en) The preparation method of three-dimensional graphite thiazolinyl tin dioxide composite material and application thereof
CN103441241A (en) Preparation method and application of prussian blue complex/carbon composite material
CN105355874A (en) Nitrogen-doped porous carbon ball/manganic manganous oxide nanometer composite electrode material and preparation method thereof
CN102386410A (en) Lithium vanadium phosphate/graphene composite material and preparation method thereof
CN104218216B (en) Molybdenum disulfide nanocomposite negative electrode material, and preparation method and use thereof
CN102142539B (en) Electrochemical insertion/deinsertion magnesium ion electrode with high capacity and stable circulation and preparation method
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
CN104129778B (en) A kind of preparation method of anode material for lithium-ion batteries functionalization graphene
Huang et al. Impact of fe doping on performance of NaTi2 (PO4) 3/C anode for aqueous lithium ion battery
CN103606672A (en) Rod-shaped nano iron oxide electrode material, and preparation method and application thereof
CN107369821A (en) A kind of ultrafast method for preparing ferroso-ferric oxide/graphene lithium ion battery composite negative pole material
CN110364705A (en) A kind of transition metals cobalt is monatomic/cluster insertion nitrogen-doped carbon framework material and its preparation method and application
CN105702958A (en) SnO2 quantum dot solution and preparation method and application of composite material thereof
Zhang et al. Green and facile synthesis of carbon encapsulated Fe3N nanospheres grown on N-doped porous carbon nanosheet as an excellent anode material
CN104091915B (en) The electrochemistry storage sodium combination electrode of a kind of high power capacity and stable circulation and preparation method
CN104600295A (en) Micron-scale spheroidal ferric fluoride positive electrode material and preparation method thereof
CN102856539A (en) Composite anode material based on CuO for lithium ion battery, its preparation method and application
CN110828819B (en) Pyrrhotite type iron sulfide negative electrode material for potassium ion battery and preparation method thereof
CN104591296A (en) High-performance hybrid crystal system ferric fluoride positive electrode material and preparation method thereof

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