CN103943837B - The preparation method of antimony oxide and composite and the application in sodium-ion battery - Google Patents

The preparation method of antimony oxide and composite and the application in sodium-ion battery Download PDF

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CN103943837B
CN103943837B CN201410145038.8A CN201410145038A CN103943837B CN 103943837 B CN103943837 B CN 103943837B CN 201410145038 A CN201410145038 A CN 201410145038A CN 103943837 B CN103943837 B CN 103943837B
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antimony oxide
antimony
oxide
metal
composite
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CN103943837A (en
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姜银珠
胡梅娟
严密
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Zhejiang University ZJU
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • 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

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  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Composite Materials (AREA)
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Abstract

The invention discloses the preparation method of antimony oxide and composite and the application in sodium-ion battery. The purposes of antimony oxide and antimony oxide composite is as anode material of lithium-ion battery, described antimony oxide composite is prepared by complex method by antimony oxide and carbon, metal or metal oxide, wherein metal comprises Ag, Au, Cu, Fe, Sn, Si, Ni, metal oxide comprises nickel oxide, cupric oxide, tin-oxide, cobalt/cobalt oxide, ferriferous oxide, Mn oxide, and wherein the shared mass percent of antimony oxide is: 50～99%. The antimony oxide of preparing by multiple effective ways and composite thereof, as anode material of lithium-ion battery, have specific capacity high, the advantage of good cycling stability, and cost of manufacture is low simultaneously, is suitable for sodium-ion battery large-scale development and application.

Description

The preparation method of antimony oxide and composite and the application in sodium-ion battery
Technical field
The present invention relates to the preparation method of a kind of antimony oxide and composite and the application in sodium-ion battery,Belong to secondary cell field.
Background technology
In recent years, lithium ion battery is because it has lightweight, high voltage, high power capacity, high-power, electric discharge is steady, advantages of environment protection, shown wide application prospect and potential great economic benefit in many-sides such as portable electric appts, electric automobile, space technology, national defense industry. But limited lithium resource and the lithium cost of material that continues to raise have limited the large-scale development of lithium ion battery.
On the other hand, the reserves of sodium element be very enrich (in the earth's crust, metallic element is number four, account for gross reserves 2.64%), and cheap, in same main group, chemical property is similar with elemental lithium, electrode potential is also more approaching. The sodium-ion battery of the function admirable therefore, obtaining with sodium replacement lithium can solve the problem of lithium TV university scale accumulate application. For this reason, the sodium electrode material of seeking high power capacity and excellent cycling performance becomes the focus that current battery research field is new.
Because the radius ratio lithium ion of sodium ion is large, the graphitic carbon negative material that reaches business application in lithium ion battery can not meet the free deintercalation of sodium ion due to its interlamellar spacing less (0.335nm), cannot be applied in sodium-ion battery. Hard carbon class material disordering, that interlamellar spacing is larger is more suitable for as anode material of lithium-ion battery, and specific capacity is the highest can reach 300mAh/g. But than alloying class negative material (as Sn, Sb, Si etc.), the specific capacity of carbon negative pole material is still lower. Application number is that 201210038789.0 Chinese invention patent discloses " a kind of anode material of lithium-ion battery ", and this patent adopts the metal that can form alloy with sodium ion as anode material of lithium-ion battery, has higher specific capacity. But alloying negative material, in the time there is alloying reaction, can produce larger volumetric expansion, Sb generates Li in lithium ion battery3The volumetric expansion producing when Sb is 260%, and in sodium-ion battery, forms Na3When Sb, volumetric expansion reaches 390%. So violent volumetric expansion will cause the efflorescence of negative material cracking, thereby from the collector inefficacy that comes off, produce larger capacity attenuation. For this reason, need under the condition that keeps alloying material height ratio capacity, slow down volumetric expansion, maintain cyclical stability.
Summary of the invention
In order to make up above-mentioned the deficiencies in the prior art, technical problem to be solved by this invention is to provide the preparation method of a kind of antimony oxide and composite and the application in sodium-ion battery.
The preparation method of antimony oxide composite is any in employing following methods:
(1) direct to described antimony oxide and material with carbon element ball milling is mixed;
(2) by described antimony oxide and sucrose, glucose or, organic polymer or slaine ball milling mix, then under protective atmosphere heat treated;
(3) adopt vapour deposition process to be coated described antimony oxide,
Described material with carbon element is one or more in graphite, acetylene black, SuperP, middle phase microballoon or RESEARCH OF PYROCARBON.
The preparation method of antimony oxide composite comprises electrostatic spray sedimentation, the precipitation method, hydro-thermal method or combustion method,
Described electrostatic spray sedimentation is: antimonic salt is dissolved in to ethanol, ethylene glycol, 1, one or more in 2-propylene glycol solvent, the metal cation precursor solution that formation concentration is 0.001～0.2mol/L, in metal cation precursor solution, add sucrose, glucose, organic polymer or slaine, after mixing, at the uniform velocity flow to spraying syringe needle, under the electrostatic field of 5～20kV, metal cation precursor solution forms the aerosol spray of stable and uniform, be deposited on heating-up temperature and be on the substrate of 100～300 DEG C and form film, by the film obtaining heat treated under protective atmosphere, obtain antimony oxide and carbon, metal or metal oxide composite,
The described precipitation method are: antimonic salt is dissolved in and in deionized water, forms homogeneous solution, in homogeneous solution, add sucrose, glucose, organic polymer or slaine, slowly drip precipitating reagent, the amount of precipitating reagent belongs to the required amount of substance calculative determination of ion generation precipitation reaction by GOLD FROM PLATING SOLUTION, formation antimony oxide precipitation, after centrifugal oven dry, obtain antimony oxide and carbon, metal or metal oxide composite, described precipitating reagent is one or more of ammoniacal liquor, NaOH, sodium carbonate;
Described hydro-thermal method is: antimonic salt and activating agent are dissolved in deionized water, form homogeneous solution, in homogeneous solution, add sucrose, glucose, organic polymer or slaine, after mixing, be transferred to and in hydrothermal reaction kettle, at 100～300 DEG C, carry out hydro-thermal reaction, reaction time is 8～30h, reaction finishes rear centrifugal oven dry and obtains antimony oxide and carbon, metal or metal oxide composite, and described activating agent is one or more in NaOH, cetab, polyvinyl acetate, oleic acid, oleyl amine;
Described combustion method is: antimony acetate and slaine are dissolved in deionized water, after fully mixing, add incendiary agent, the mol ratio of incendiary agent and metal ion is 0.5:1～4:1, after fully mixing, add again ammoniacal liquor regulator solution pH to 7, solution is placed in to water-bath adds thermal agitation until form the gel of thickness, this gel is placed in and is warming up in advance the Muffle furnace of 200～500 DEG C and carries out combustion reaction, and be incubated 1 hour, obtain antimony oxide and metal or metal oxide composite, described incendiary agent is citric acid, glycine, urea, ethylene glycol, alanine, ammonium acetate, butanedioic acid, one or more in monoethanolamine,
Described antimonic salt is antimony acetate, antimony chloride, potassium antimony tartrate, antimony fluoride or antimony trisulfide.
Described antimony oxide composite is as anode material of lithium-ion battery.
Described antimony oxide composite is prepared by complex method by antimony oxide and carbon, metal or metal oxide, wherein metal comprises Ag, Au, Cu, Fe, Sn, Si, Ni, metal oxide comprises nickel oxide, cupric oxide, tin-oxide, cobalt/cobalt oxide, ferriferous oxide, Mn oxide, and wherein the shared mass percent of antimony oxide is: 50～99%.
The new purposes of antimony oxide is that described antimony oxide is used as anode material of lithium-ion battery.
The antimony oxide that the present invention adopts and composite thereof are as anode material of lithium-ion battery, first there is conversion reaction with sodium ion, generate simple substance antimony and sodium oxide molybdena, antimony and sodium generation alloying reaction subsequently, the sodium oxide molybdena that conversion reaction generates can be alleviated the volumetric expansion in follow-up alloying process, the theoretical specific capacity that calculates antimony oxide by two-step reaction can reach 1103mAh/g, and the theoretical specific capacity of simple substance antimony is only 660mAh/g. Meanwhile, the molal volume of antimony oxide is larger than simple substance antimony, and the volumetric expansion that under equal conditions, alloying produces changes also little than simple substance antimony. In addition, antimony oxide is also further alleviated to volumetric expansion and efflorescence cracking phenomena with the compound meeting of other materials. The antimony oxide of preparing by multiple effective ways and composite thereof, as anode material of lithium-ion battery, have specific capacity high, the advantage of good cycling stability, and cost of manufacture is low simultaneously, is suitable for sodium-ion battery large-scale development and application.
Brief description of the drawings
Fig. 1 is Sb prepared by the embodiment of the present invention 12O3The X ray diffracting spectrum of material
Fig. 2 is Sb prepared by the embodiment of the present invention 12O3The stereoscan photograph of material
Fig. 3 is Sb prepared by the embodiment of the present invention 12O3The charging and discharging curve figure of material
Fig. 4 is Sb prepared by the embodiment of the present invention 12O3Material cycle performance curve.
Detailed description of the invention
Further illustrate the present invention below by specific embodiment, still, should be understood to, these embodiment are only used for specifically describing more in detail use, and should not be construed as for limiting in any form the present invention.
General description is carried out to the material and the test method that use in the present invention's experiment in this part. Although be well known in the art for realizing many materials and the method for operating that the object of the invention uses, the present invention still does to describe in detail as far as possible at this. It will be apparent to those skilled in the art that in context, if not specified, material therefor of the present invention and method of operating are well known in the art.
Embodiment 1
The present embodiment adopts electrostatic spray deposition to prepare antimony oxide anode material of lithium-ion battery, and concrete steps are:
Antimony acetate is dissolved in the mixed solvent of ethanol/ethylene glycol (volume ratio is 4:1), the precursor solution that formation concentration is 0.01mol/L, precursor solution is at the uniform velocity flowed to spraying syringe needle with 3ml/h, adjustable spraying syringe needle is 4cm to the distance of substrate, under the electrostatic field of 7kV, precursor solution forms the aerosol spray of stable and uniform, be deposited on heating-up temperature and be at the bottom of the stainless steel lining of 160 DEG C on, control sedimentation time is 240min, obtains antimony oxide film.
Be that anode material of lithium-ion battery is prepared into sodium-ion battery by above-mentioned antimony oxide film. This antimony oxide film can, directly as negative material, as collector, not need the pulping process of binding agent and conductive agent cooperation at the bottom of stainless steel lining. In the glove box that is assemblied in argon gas atmosphere of concrete battery, carry out, using sodium metal sheet as to electrode, the NaPF of 1M6(EC:DEC=1:1) solution, as electrolyte, taking Celgard2300 as barrier film, is assembled into 2025 button cells. Battery charging and discharging experiment is used constant current charge-discharge pattern to carry out on new prestige (Neware) battery test system, and voltage tester scope is 0.01～2V. Test. Fig. 3 is the charging and discharging curve in first three week of antimony oxide film cathode material, as shown in Figure 3, is under 500mA/g in current density, and the reversible capacity of material is 331mAh/g. Through circulation in 150 weeks, capacity reached 432mAh/g
Embodiment 2
The present embodiment adopts ball-milling method to prepare antimony oxide/carbon composite, and concrete steps are:
Be 7:3 by antimony oxide powder and SuperP(mass ratio) 500 revs/min of ball milling mixing 6h in the ball grinder of applying argon gas, obtain the coated antimony oxide/carbon composite of carbon, wherein the shared mass fraction of antimony oxide is 70%.
Above-mentioned composite is prepared into sodium-ion battery. Concrete steps are: by the antimony oxide powder and the acetylene black that prepare, binding agent PVDF(Kynoar) mix according to the weight ratio of 80:10:10, add appropriate NMP(N-methyl pyrrolidone) the ultrasonic dispersion of solution, after stirring, forming slurry is coated on Copper Foil, after dry, be cut into the pole piece of Φ=15mm, under vacuum condition in 120 DEG C dry 10 hours, be transferred at random glove box for subsequent use. The assembling process method of testing of button cell is with embodiment 1.
Embodiment 3
The present embodiment adopts ball-milling method to prepare antimony oxide/ferric oxide composite material, and concrete steps are:
By 500 revs/min of ball milling mixing 10h of antimony oxide powder and ferric nitrate (mass ratio is 1:5) ball milling, by mixed-powder heat treatment 5h at 300 DEG C, obtain antimony oxide/ferric oxide composite material, wherein the shared mass fraction of antimony oxide is about 50%.
Embodiment 4
The present embodiment adopts chemical vapour deposition technique to prepare antimony oxide/Ag composite, and concrete steps are:
Antimony oxide film prepared by embodiment 1 is as substrate, taking ethanol as solvent, configuration concentration is the liquor argenti nitratis ophthalmicus of 0.005mol/L, be injected into the evaporation region of reaction cavity by impulse jet nozzle using this solution as source solution, pulse frequency is 3Hz, single pulse injecting time is 50ms, transport speed mL/min, keep evaporation region, transport region and substrate temperature is, using nitrogen in carrier gas passes into reative cell, flow-control is at 1200sccm, and system pressure remains on 40mbar, and sedimentation time is 120min. Obtain antimony oxide/Ag composite, wherein Ag is coated on antimony oxide particle surface, accounts for 1% of gross mass mark, contributes to improve the electric conductivity of antimony oxide, can alleviate the volumetric expansion in charge and discharge process simultaneously.
Embodiment 5
The present embodiment adopts the precipitation method to prepare antimony oxide anode material of lithium-ion battery, and it is carried out to the coated processing of carbon, and concrete steps are:
Potassium antimony tartrate is dissolved in to the homogeneous solution that forms 0.1mol/L in deionized water, then the ammoniacal liquor of 0.1mol/L is slowly added drop-wise to and in homogeneous solution, forms antimony oxide precipitation. To precipitate centrifugally, then use deionized water rinsing, in triplicate after filtering drying, obtain antimony oxide dusty material. By this antimony oxide powder and sucrose (mass ratio is 5:1) 300 revs/min of ball milling mixing 4h in the ball grinder of applying argon gas, carry out pyrolysis at 600 DEG C of heating 4h again, after cooling, obtain the coated antimony oxide negative material of carbon, wherein the shared mass fraction of carbon is about 7.0%.
Embodiment 6
The present embodiment adopts hydro-thermal method to prepare antimony oxide/tin ash composite, and concrete steps are:
0.342g trichloride antimony and 0.130g butter of tin are dissolved in 10ml ethanol, then add 0.2gCTAB to form homogeneous solution. Then, sodium hydroxide solution (0.300gNaOH is dissolved in 15ml deionized water) is slowly added drop-wise in homogeneous solution, after mixing, mixed solution is transferred in hydrothermal reaction kettle and is sealed, be placed at 160 DEG C and react 12h. In the time that reactor is cooled to room temperature, by centrifugal the product obtaining, with deionized water or alcohol cleaning several, finally dry and obtain antimony oxide/tin ash composite, wherein the shared mass fraction of antimony oxide is 74.3%.
Embodiment 7
The present embodiment adopts combustion method to prepare antimony oxide/cupric oxide composite, and it is carried out to the coated processing of carbon, and concrete steps are:
Antimony acetate and copper nitrate (mol ratio is 3:1) are dissolved in deionized water, after fully mixing, add citric acid, the mol ratio of citric acid and metal ion is 3:1, adds ammoniacal liquor regulator solution pH to 7 after fully mixing again. Solution is placed in to water-bath adds thermal agitation 4 hours until form the gel of thickness. This gel is placed in and is warming up in advance the Muffle furnace of 400 DEG C and carries out combustion reaction, and be incubated 1 hour, obtain fluffy antimony oxide/cupric oxide powder. Wherein the shared mass fraction of antimony oxide is 84.6%.
Above-described embodiment is to explain in detail for more of the present invention; but obviously; the researcher in the technology of the present invention field can make the change of pattern aspect unsubstantiality and not depart from the scope that institute of the present invention essence is protected according to the above embodiments, such as Sb2O3And Sb2O3/ C material is simultaneously for making anode material of lithium-ion battery; Or fructose etc. are as organic carbon source.

Claims (3)

1. a preparation method for antimony oxide composite, is characterized in that comprising electrostatic spray sedimentation or combustion method,
Described electrostatic spray sedimentation is: antimonic salt is dissolved in to ethanol, ethylene glycol, 1, one or more in 2-propane diols, the metal cation precursor solution that formation concentration is 0.001～0.2mol/L, in metal cation precursor solution, add sucrose, glucose, organic polymer or slaine, after mixing, at the uniform velocity flow to spraying syringe needle, under the electrostatic field of 5～20kV, metal cation precursor solution forms the aerosol spray of stable and uniform, be deposited on heating-up temperature and be on the substrate of 100～300 DEG C and form film, by the film obtaining heat treated under protective atmosphere, obtain antimony oxide and carbon, antimony oxide and metal or antimony oxide and metal oxide composite,
Described combustion method is: antimony acetate and slaine are dissolved in deionized water, after fully mixing, add incendiary agent, the mol ratio of incendiary agent and metal ion is 0.5:1～4:1, after fully mixing, add again ammoniacal liquor regulator solution pH to 7, solution is placed in to water-bath adds thermal agitation until form the gel of thickness, this gel is placed in and is warming up in advance the Muffle furnace of 200～500 DEG C and carries out combustion reaction, and be incubated 1 hour, obtain antimony oxide and metal oxide composite, described incendiary agent is citric acid, glycine, urea, ethylene glycol, alanine, ammonium acetate, butanedioic acid, one or more in monoethanolamine,
Described antimonic salt is antimony acetate, antimony chloride, potassium antimony tartrate, antimony fluoride or antimony trisulfide;
Metal in described slaine is Ag, Au, Cu, Fe, Sn or Ni.
2. a purposes for the antimony oxide composite that as claimed in claim 1 prepared by method, is characterized in that described antimony oxide composite is as anode material of lithium-ion battery.
3. the purposes of antimony oxide composite according to claim 2, is characterized in that the shared mass percent of antimony oxide is: 50～99%.
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Families Citing this family (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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CN107022110B (en) * 2017-05-18 2018-07-31 三斯达（江苏）环保科技有限公司 The preparation of compound antimony oxide and its application in high flame retardant EVA expanded materials
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CN108336337B (en) * 2018-02-08 2021-08-17 魏阅文 Sodium ion battery negative electrode material C/Sb2O3Preparation and application of/C composite hollow sphere material
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CN110380038B (en) * 2019-07-24 2020-09-01 东北大学秦皇岛分校 Pyrolytic carbon composite material embedded with multi-shell antimony oxide-antimony alloy and preparation method thereof
CN111029553A (en) * 2019-12-25 2020-04-17 溧阳中科海钠科技有限责任公司 Sodium-ion battery positive electrode material and preparation method and application thereof
CN111342049A (en) * 2020-03-04 2020-06-26 溧阳中科海钠科技有限责任公司 Modified sodium ion battery positive electrode material, preparation method and battery
CN114267830B (en) * 2021-12-13 2024-06-11 荆门亿纬创能锂电池有限公司 Method for preparing antimony-loaded silicon-carbon composite negative electrode material by adopting peanut shell, composite negative electrode material and lithium ion battery
CN114649508B (en) * 2022-04-07 2023-04-07 中国科学院长春应用化学研究所 Antimony-based integrated electrode and preparation method and application thereof
CN115050920B (en) * 2022-06-15 2024-01-30 中国科学院长春应用化学研究所 Antimony-based integrated electrode and preparation method and application thereof
CN115832328A (en) * 2023-02-08 2023-03-21 南方科技大学 Porous carbon electrode, preparation method thereof and flow battery

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1198022A (en) * 1997-04-24 1998-11-04 松下电器产业株式会社 Non aqueous electrolyte secondary batteries
CN101325253A (en) * 2007-06-13 2008-12-17 中国科学院金属研究所 Method for preparing cathode material for high capacity lithium ion battery

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1198022A (en) * 1997-04-24 1998-11-04 松下电器产业株式会社 Non aqueous electrolyte secondary batteries
CN101325253A (en) * 2007-06-13 2008-12-17 中国科学院金属研究所 Method for preparing cathode material for high capacity lithium ion battery

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
"Direct synthesis of Sb2O3 nanoparticles via hydrolysis-precipitation method";Yuehua Hu 等;《Journal of Alloys and Compounds》;20060519;第428卷;第327-331页 *
"High capacity Sb2O4 thin film electrodes for rechargeable sodium battery";Qian Sun 等;《Electrochemistry Communications》;20111001;第13卷;第1462-1464页 *
"Hydrothermal synthesis of morphology-controllable Sb2O3 Hollow spindle-like and cobblestone-like microstructures";Shengsong Ge 等;《Applied Surface Science》;20101123;第257卷;第3657-3665页 *

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