CN103904327A - Preparation method of high-performance lithium ion battery negative material Mn2OBO3 - Google Patents

Preparation method of high-performance lithium ion battery negative material Mn2OBO3 Download PDF

Info

Publication number
CN103904327A
CN103904327A CN201410163758.7A CN201410163758A CN103904327A CN 103904327 A CN103904327 A CN 103904327A CN 201410163758 A CN201410163758 A CN 201410163758A CN 103904327 A CN103904327 A CN 103904327A
Authority
CN
China
Prior art keywords
obo
preparation
presoma
hours
performance 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
CN201410163758.7A
Other languages
Chinese (zh)
Other versions
CN103904327B (en
Inventor
徐立强
李爱华
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.)
Shandong University
Original Assignee
Shandong University
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 University filed Critical Shandong University
Priority to CN201410163758.7A priority Critical patent/CN103904327B/en
Publication of CN103904327A publication Critical patent/CN103904327A/en
Application granted granted Critical
Publication of CN103904327B publication Critical patent/CN103904327B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B35/00—Boron; Compounds thereof
    • C01B35/08—Compounds containing boron and nitrogen, phosphorus, oxygen, sulfur, selenium or tellurium
    • C01B35/10—Compounds containing boron and oxygen
    • C01B35/12—Borates
    • 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
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Nanotechnology (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Materials Engineering (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention relates to a preparation method of a high-performance lithium ion battery negative material Mn2OBO3. The preparation method comprises the following steps of dissolving a boron source into the solvent which is one or the combination of more than two of water, methanol, ethanol, glycol, propanediol, tetraglycol and pentanol to be stirred, and heating the mixture for 20 hours to 24 hours under the condition of 200 to 220 DEG C to obtain a precursor; and calcining the precursor for 5 hours to 12 hours at the temperature of 600 to 750 DEG C to obtain the Mn2OBO3 nano material. The preparation method has the advantages of simplicity in operation, low reaction temperature, small energy consumption, controllability in product appearance and the like. By adopting the simple solvent heating-calcining method, the Mn2OBO3 material in different shapes can be synthesized by selecting different solvent raw materials, and the obtained Mn2OBO3 material has stable electrochemical performance.

Description

A kind of high performance lithium ionic cell cathode material Mn 2oBO 3preparation method
Technical field
The present invention relates to a kind of high performance lithium ionic cell cathode material Mn 2oBO 3preparation method, belong to electrochemistry and new energy materials technical field.
Background technology
Service life cycle is long, safe because having for lithium rechargeable battery, memory-less effect, volume are little, specific energy advantages of higher is widely used in the digital product such as mobile phone, notebook computer.But lithium ion battery can't meet the application in electric automobile field, main restraining factors are exactly specific capacity, stable circulation, fail safe etc.The key that improves performance of lithium ion battery is to improve the performance of electrode material.So far, the negative material that is actually used in lithium ion battery is all carbon materials substantially, can not meet the growing demand of people but material with carbon element specific capacity is low, and therefore the negative material of other except material with carbon element has caused people's extensive concern.Wherein borate material becomes the focus in lithium ion battery negative material field because it has the theoretical capacity higher than commercialization graphite material and aboundresources advantages of environment protection.
Calendar year 2001, Nazar seminar reported first FeBO 3chemical property.Report that at present borate negative material mainly contains Fe 3bO 6(Journal of power sources, 2001,97,254-257; RSC Advance, 2014,4,8245 – 8249), Cr 3bO 6(Journal of Materials Chemistry, 2001,11,3228-3233), VBO 3(Journal of power sources, 2003,119,621-625) and M 3b 2o 6(M=Co, Ni, Cu) (Chemistry of Materials, 2003,15,3683-3691).Although above-mentioned different materials all has higher initial capacity, after the certain number of turns of circulation, capacity attenuation is serious, and cyclical stability is poor.In addition, current reported borate negative material all synthesizes by high temperature solid-state method substantially, and the reaction time is long, energy consumption is large and product is mostly the graininess that there is no pattern.Therefore easier synthetic method and the good borate negative material of synthesising stability, explored except solid phase method are new challenges.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of high performance lithium ionic cell cathode material Mn 2oBO 3preparation method, preparation method of the present invention is easy and be easy to industrialization, has improved performance of lithium ion battery.
Technical scheme of the present invention is as follows:
A kind of high performance lithium ionic cell cathode material Mn 2oBO 3preparation method, comprise the steps:
(1) with water, methyl alcohol, ethanol, ethylene glycol, propylene glycol, wherein one or the arbitrarily two or more solvents that are combined as in tetraethylene glycol or n-amyl alcohol, boron source is added in solvent, the addition in boron source with the molal volume of solvent ratio is: (0.5～2.5): (0.5～2.5), unit: mol/L, then in boron source: the mol ratio in manganese source is (1～4): 1 ratio adds manganese source, stir 0.5～3 hour, be transferred in polytetrafluoroethylene reactor, with putting into baking oven after the sealing of stainless steel still shell, under 200～220 DEG C of conditions, heat 20～24 hours, after being cooled to room temperature, carry out suction filtration or centrifuge washing, dry 4～6 hours in 60～80 DEG C, obtain presoma,
(2), by step (1) gained presoma, in air atmosphere, 600-750 DEG C of calcining 5-12 hour, obtains Mn 2oBO 3nano material.
The present invention is preferred, uses different solvents can obtain the Mn of different-shape 2oBO 3nano material, is used deionized water to obtain Mn 2oBO 3nanometer rods, is used ethanol to obtain Mn 2oBO 3nano rod bundle.
The present invention is preferred, and in the time that solvent is deionized water, the addition of deionized water is 40～80mL, makes Mn 3b 7o 13oH nanometer rods presoma, Mn 3b 7o 13the long 10-20 micron of OH nanometer rods presoma, average diameter 200 nanometers, in air atmosphere, 600-750 DEG C of calcining made Mn after 5-12 hour 2oBO 3nanometer rods, gained Mn 2oBO 3nanometer rods diameter is constant, and length is 150-1000 nanometer.
The present invention is preferred, and in the time that solvent is ethanol, ethanol consumption is 40～80mL, makes MnBO 2oH nano rod bundle presoma, MnBO 2the long 10-15 micron of OH nano rod bundle, average diameter 350 nanometers, in air atmosphere, 600-750 DEG C of calcining, after 5-12 hour, makes Mn 2oBO 3nano rod bundle, gained Mn 2oBO 3nano rod bundle diameter is constant, and entire length is constant, and the stub that is 200-500 nanometer by more piece length is joined together to form nano rod bundle.
The present invention is preferred, and step (1) is heated to 200～220 DEG C taking heating rate as 5～7 DEG C/min.
The present invention is preferred, and the boron source described in step (1) is wherein a kind of or two or more combination arbitrarily in boric acid, ammonium borate or borax.
The present invention is further preferred, and described boron source is boric acid or ammonium borate.
The present invention is preferred, and the manganese source described in step (1) is a kind of of manganese carbonate, manganese nitrate aqueous solution, manganese acetate, manganese dioxide, manganous oxide or manganese sulfate or two or more combination arbitrarily.
The present invention is further preferred, and described manganese source is manganese nitrate aqueous solution, and the mass fraction of manganese nitrate aqueous solution is 50wt%.
The present invention is preferred, and in step (1), described suction filtration is under vacuum degree 0.1MPa condition, with the each washing of deionized water and ethanol 2～3 times, centrifuge washing is under rotating speed 5000～6000r/min condition, uses the each washing of deionized water and ethanol 2～3 times, washs 3～5 minutes at every turn.
The present invention is preferred, and step (2) is heated to 600-750 DEG C taking heating rate as 3～5 DEG C/min.
The present invention is preferred, the purity >=99.7wt% of described methyl alcohol, ethanol, ethylene glycol, propylene glycol, tetraethylene glycol or n-amyl alcohol.
Preferred according to the present invention, a kind of high performance lithium ionic cell cathode material Mn 2oBO 3preparation method, step is as follows:
(1) 0.01～0.04mol ammonium borate is joined in 10～40mL deionized water, stir it is dissolved, obtain ammonium borate solution, the Mn (NO that is 50wt% by 0.01～0.03mol mass concentration 3) 2solution drops in ammonium borate solution, then add 10～40mL deionized water, stir 1 hour, be transferred in the polytetrafluoroethylkettle kettle of 60～100mL, stainless steel still shell sealing for polytetrafluoroethylkettle kettle, polytetrafluoroethylkettle kettle is put into the baking oven of 200～220 DEG C, heat 20～24 hours, be cooled to room temperature, carry out suction filtration or centrifuge washing processing, dry 4～6 hours, obtain Mn for 60～80 DEG C 3b 7o 13oH nanometer rods presoma;
(2) by Mn 3b 7o 13oH nanometer rods presoma is put into resistance furnace, in air atmosphere, is raised to 600～750 DEG C with 5 DEG C/min heating rate, calcines 10～12 hours, naturally cools to room temperature, obtains Mn 2oBO 3nanometer rods.
Preferred according to the present invention, a kind of high performance lithium ionic cell cathode material Mn 2oBO 3preparation method,
(1) 0.01～0.04mol ammonium borate is joined in 10～40mL ethanol, stir it is dissolved, obtain ammonium borate solution, the Mn (NO that is 50wt% by the mass concentration of 0.01～0.03mol 3) 2solution drops in ammonium borate solution, add 10～40mL ethanol, stir 1 hour, be transferred in the polytetrafluoroethylkettle kettle of 60～100mL, stainless steel still shell sealing for polytetrafluoroethylkettle kettle, polytetrafluoroethylkettle kettle is put into the baking oven of 200～220 DEG C, heat 12～24 hours, be cooled to room temperature, carry out suction filtration or centrifuge washing processing, dry 4～6 hours, obtain MnBO for 60～80 DEG C 2oH nano rod bundle presoma;
(2) by MnBO 2oH nano rod bundle presoma is put into resistance furnace, in air atmosphere, is raised to 650～750 DEG C with 5 DEG C/min heating rate, calcines 5～7 hours, naturally cools to room temperature, obtains Mn 2oBO 3nano rod bundle.
Advantage of the present invention is as follows:
(a) the present invention has the advantages such as simple to operate, reaction temperature is low, energy consumption is little, product pattern is controlled.Adopt the method for simple solvent heat-calcining, by selecting different solvent raw material etc. to control the Mn of synthetic different-shape 2oBO 3material, and obtained the good chemical property of stability.
(b) simple and easy to get, cheap, the environmental friendliness of raw material used herein, reaction time is short, temperature is lower, only need can carry out next step calcining in the lower solvent heat treatment of lower temperature (220 DEG C), energy consumption is little, in enormous quantities low-cost production.
(c) products therefrom of the present invention, without carrying out reprocessing, generates without poisonous and harmful substance in course of reaction.
Brief description of the drawings
Fig. 1 is the Mn in embodiment 1 and embodiment 2 preparation process 3b 7o 13oH nanometer rods presoma and MnBO 2xRD figure and the SEM photo of OH nano rod bundle presoma.
Wherein, Fig. 1 a is the Mn in embodiment 1 and embodiment 2 preparation process 3b 7o 13oH nanometer rods presoma and MnBO 2the XRD figure of OH nano rod bundle presoma, wherein left ordinate is intensity, abscissa is angle of diffraction (2 θ),
Fig. 1 b is the Mn in embodiment 1 preparation process 3b 7o 13the SEM photo of OH nanometer rods presoma,
Fig. 1 c is the MnBO in embodiment 2 preparation process 2the SEM photo of OH nano rod bundle presoma,
Fig. 2 is Mn in embodiment 1 and embodiment 2 3b 7o 13oH nanometer rods presoma and MnBO 2mn corresponding to end-product that OH nano rod bundle presoma obtains after calcining 2oBO 3nanometer rods and Mn 2oBO 3xRD figure and the SEM photo of nano rod bundle.
Wherein, Fig. 2 a is Mn in embodiment 1 and embodiment 2 3b 7o 13oH nanometer rods presoma and MnBO 2the end-product Mn that OH nano rod bundle presoma obtains after calcining 2oBO 3nanometer rods and Mn 2oBO 3the XRD figure of nano rod bundle, wherein left ordinate is intensity, abscissa is angle of diffraction (2 θ),
Fig. 2 b is the end-product Mn of embodiment 1 2oBO 3the SEM photo of nanometer rods, with the Mn of Fig. 1 b 3b 7o 13oH presoma is compared, end-product Mn 2oBO 3though nanometer rods size reduction, the pattern of nanometer rods has obtained maintenance.
Fig. 2 c is the end-product Mn of embodiment 2 2oBO 3the SEM photo of the SEM photo of nano rod bundle, with the MnBO of Fig. 1 c 2oH presoma is compared, end-product Mn 2oBO 3nano rod bundle overall dimensions is substantially constant, is formed by connecting but the nanometer rods of composition nano rod bundle becomes a section short nanometer rods, and the pattern of overall nano rod bundle has also obtained maintenance.
Fig. 3 is the end-product Mn of embodiment 1 2oBO 3the end-product Mn of nanometer rods and embodiment 2 2oBO 3nano rod bundle electrochemical property test result.
Wherein Fig. 3 a is cycle performance figure, and Fig. 3 b is high rate performance figure, and the left ordinate of two figure is all specific capacities, specific capacity unit: every gram of MAH (mAh/g), abscissa is all the circulation number of turns (n).
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be appreciated that, these examples are only not used in and limit the scope of the invention for the present invention is described.In addition should be understood that, after having read content set forth in the present invention, those skilled in the art can make various changes or modifications the present invention, these equivalent form of values fall within the application's appended claims limited range equally.
The equipment polytetrafluoroethylkettle kettle using in embodiment, purchased from Yongtai, Jinan plastic cement Co., Ltd.
Raw material NH 4hB 4o 7﹒ 3H 2o, Mn (NO 3) 2(aqueous solution that mass fraction is 50%) is existing commercial product,
NH 4hB 4o 7, Mn (NO 3) 2(aqueous solution that mass fraction is 50%) is purchased from Shanghai traditional Chinese medicines group.
Embodiment 1
Mn 2oBO 3the preparation of nano-bar material
By 0.01mol NH 4hB 4o 7﹒ 3H 2o is dissolved in 20mL deionized water, then by the Mn (NO of 0.01mol mass concentration 50wt% 3) 2the aqueous solution splashes in above-mentioned solution, finally adds 20mL deionized water, fully stirs and evenly mixs after 1 hour, be transferred in 60mL polytetrafluoroethylkettle kettle, react 24 hours with the baking oven of putting into 220 DEG C after stainless steel still shell sealing, carry out suction filtration after being cooled to room temperature, obtain Mn 3b 7o 13oH nanometer rods presoma.By Mn 3b 7o 13oH nanometer rods presoma is placed in the lower 750 DEG C of calcinings of resistance furnace air atmosphere and within 12 hours, obtains Mn 2oBO 3nanometer rods.Gained Mn 3b 7o 13oH nanometer rods presoma and end product Mn 2oBO 3the XRD of nanometer rods and SEM photo result, as shown in Fig. 1 a, Fig. 1 b, Fig. 2 a, Fig. 2 b, can be found out the Mn that gained presoma and end product are pure phase in the XRD figure from Fig. 1 a, Fig. 2 a 3b 7o 13oH and Mn 2oBO 3, from Fig. 1 b, can find out Mn 3b 7o 13oH is that nanometer rods and output are higher, from Fig. 2 b, can find out end-product Mn 2oBO 3though nanometer rods size reduction, the pattern of nanometer rods has obtained maintenance.
Embodiment 2
Mn 2oBO 3the preparation of nano rod bundle material
By 0.01mol NH 4hB 4o 7﹒ 3H 2o is dissolved in 20mL ethanol, then by the Mn (NO of 0.01mol mass concentration 50wt% 3) 2solution splashes in above-mentioned solution, finally adds 20mL ethanol, fully stirs and evenly mixs after 1 hour, is transferred in 60mL polytetrafluoroethylkettle kettle, reacts 12 hours with the baking oven of putting into 220 DEG C after stainless steel still shell sealing, carries out suction filtration after being cooled to room temperature, obtains MnBO 2oH nano rod bundle presoma.By MnBO 2oH nano rod bundle presoma is placed in the lower 700 DEG C of calcinings of resistance furnace air atmosphere and within 5 hours, obtains Mn 2oBO 3nano rod bundle.Gained MnBO 2oH nano rod bundle presoma and end product Mn 2oBO 3the XRD of nano rod bundle and SEM photo result, as shown in Fig. 1 a, Fig. 1 c, Fig. 2 a, Fig. 2 c, can be found out the MnBO that gained presoma and end product are pure phase in the XRD figure from Fig. 1 a, Fig. 2 a 2oH and Mn 2oBO 3, from Fig. 1 c, can find out MnBO 2oH is that nano rod bundle and output are higher.From Fig. 2 c, can find out end-product Mn 2oBO 3nano rod bundle overall dimensions is substantially constant, is formed by connecting but the nanometer rods of composition nano rod bundle becomes a section short nanometer rods, and the pattern of overall nano rod bundle has also obtained maintenance.
Electrochemical property test
Product prepared by embodiment 1, embodiment 2, as lithium ion battery negative material, adopts rubbing method to prepare electrode, by raw material Mn in mass ratio 2oBO 3: the ratio of acetylene black: CMC=70:20:10 is mixed, and taking water as solvent, makes cathode size, is coated on Copper Foil, and after fully dry compressing tablet, section obtains the negative plate that diameter is 12mm.Battery cathode sheet lithium sheet.In the glove box of inert gas shielding, taking the LiPF6/EC/DMC/DEC (1:1:1) of 1mol/L as electrolyte, Celgerd2300 is barrier film, is assembled into 2320 type button cells.Tester: discharge and recharge instrument (Land); Bruker D8-X x ray diffractometer x.On blue electric tester, carry out Mn 2oBO 3battery charging/discharging performance testing, discharges and recharges condition: in 0.01～3.0 voltage range, and when current density is 100mA/g, Mn 2oBO 3nanometer rods and nano rod bundle initial discharge capacity are respectively 1172 and 1037mAh/g, can be stabilized in respectively 600 and 554mAh/g, as shown in Figure 3 a after 50 circles circulations.Under different current densities, material is carried out to high rate performance test, Mn 2oBO 3nanometer rods and nano rod bundle have all shown extraordinary invertibity, stability and recovery.Result as shown in Figure 3 b.
Embodiment 3
Other patterns Mn 2oBO 3the preparation of material
By 0.01mol NH 4hB 4o 7﹒ 3H 2o is dissolved in 20mL tetraethylene glycol, then by the Mn (NO of 0.01mol mass concentration 50wt% 3) 2the aqueous solution splashes in above-mentioned solution, finally adds 20mL tetraethylene glycol, fully stirs and evenly mixs after 1 hour, be transferred in 60mL polytetrafluoroethylkettle kettle, react 24 hours with the baking oven of putting into 220 DEG C after stainless steel still shell sealing, carry out centrifuge washing processing after being cooled to room temperature, obtain Mn 3b 7o 13oH triangle presoma.By Mn 3b 7o 13oH triangle presoma is placed in lower 700 DEG C of resistance furnace air atmosphere and calcines the Mn that obtains triangle for 5 hours 2oBO 3.

Claims (10)

1. a high performance lithium ionic cell cathode material Mn 2oBO 3preparation method, comprise the steps:
(1) with water, methyl alcohol, ethanol, ethylene glycol, propylene glycol, wherein one or the arbitrarily two or more solvents that are combined as in tetraethylene glycol or n-amyl alcohol, boron source is added in solvent, the addition in boron source with the molal volume of solvent ratio is: (0.5～2.5): (0.5～2.5), unit: mol/L, then in boron source: the mol ratio in manganese source is (1～4): 1 ratio adds manganese source, stir 0.5～3 hour, be transferred in polytetrafluoroethylene reactor, with putting into baking oven after the sealing of stainless steel still shell, under 200～220 DEG C of conditions, heat 20～24 hours, after being cooled to room temperature, carry out suction filtration or centrifuge washing, dry 4～6 hours in 60～80 DEG C, obtain presoma,
(2), by step (1) gained presoma, in air atmosphere, 600-750 DEG C of calcining 5-12 hour, obtains Mn 2oBO 3nano material.
2. high performance lithium ionic cell cathode material Mn according to claim 1 2oBO 3preparation method, it is characterized in that, in the time that solvent is deionized water, the addition of deionized water is 40～80mL, makes Mn 3b 7o 13oH nanometer rods presoma, Mn 3b 7o 13the long 10-20 micron of OH nanometer rods presoma, average diameter 200 nanometers, in air atmosphere, 600-750 DEG C of calcining made Mn after 5-12 hour 2oBO 3nanometer rods, gained Mn 2oBO 3nanometer rods diameter is constant, and length is 150-1000 nanometer; In the time that solvent is ethanol, ethanol consumption is 40～80mL, makes MnBO 2oH nano rod bundle presoma, MnBO 2the long 10-15 micron of OH nano rod bundle, average diameter 350 nanometers, in air atmosphere, 600-750 DEG C of calcining, after 5-12 hour, makes Mn 2oBO 3nano rod bundle, gained Mn 2oBO 3nano rod bundle diameter is constant, and entire length is constant, and the stub that is 200-500 nanometer by more piece length is joined together to form nano rod bundle.
3. high performance lithium ionic cell cathode material Mn according to claim 1 2oBO 3preparation method, it is characterized in that, step (1) is heated to 200～220 DEG C taking heating rate as 5～7 DEG C/min.
4. high performance lithium ionic cell cathode material Mn according to claim 1 2oBO 3preparation method, it is characterized in that, the boron source described in step (1) is wherein a kind of or arbitrarily two or more combination in boric acid, ammonium borate or borax, further preferred, described boron source is boric acid or ammonium borate.
5. high performance lithium ionic cell cathode material Mn according to claim 1 2oBO 3preparation method, it is characterized in that, manganese source described in step (1) is a kind of of manganese carbonate, manganese nitrate aqueous solution, manganese acetate, manganese dioxide, manganous oxide or manganese sulfate or two or more combination arbitrarily, further preferred, described manganese source is for being manganese nitrate aqueous solution, and the mass fraction of manganese nitrate aqueous solution is 50wt%.
6. high performance lithium ionic cell cathode material Mn according to claim 1 2oBO 3preparation method, it is characterized in that, in step (1), described suction filtration is under vacuum degree 0.1MPa condition, with the each washing of deionized water and ethanol 2～3 times, centrifuge washing is under rotating speed 5000～6000r/min condition, uses the each washing of deionized water and ethanol 2～3 times, washs 3～5 minutes at every turn.
7. high performance lithium ionic cell cathode material Mn according to claim 1 2oBO 3preparation method, it is characterized in that, step (2) is heated to 600-750 DEG C taking heating rate as 3～5 DEG C/min.
8. high performance lithium ionic cell cathode material Mn according to claim 1 2oBO 3preparation method, it is characterized in that the purity>=99.7wt% of described methyl alcohol, ethanol, ethylene glycol, propylene glycol, tetraethylene glycol or n-amyl alcohol.
9. high performance lithium ionic cell cathode material Mn according to claim 1 2oBO 3preparation method, it is characterized in that, step is as follows:
(1) 0.01～0.04mol ammonium borate is joined in 10～40mL deionized water, stir it is dissolved, obtain ammonium borate solution, the Mn (NO that is 50wt% by 0.01～0.03mol mass concentration 3) 2solution drops in ammonium borate solution, then add 10～40mL deionized water, stir 1 hour, be transferred in the polytetrafluoroethylkettle kettle of 60～100mL, stainless steel still shell sealing for polytetrafluoroethylkettle kettle, polytetrafluoroethylkettle kettle is put into the baking oven of 200～220 DEG C, heat 20～24 hours, be cooled to room temperature, carry out suction filtration or centrifuge washing processing, dry 4～6 hours, obtain Mn for 60～80 DEG C 3b 7o 13oH nanometer rods presoma;
(2) by Mn 3b 7o 13oH nanometer rods presoma is put into resistance furnace, in air atmosphere, is raised to 600～750 DEG C with 5 DEG C/min heating rate, calcines 10～12 hours, naturally cools to room temperature, obtains Mn 2oBO 3nanometer rods.
10. high performance lithium ionic cell cathode material Mn according to claim 1 2oBO 3preparation method, it is characterized in that, step is as follows: (1) joins 0.01～0.04mol ammonium borate in 10～40mL ethanol, stir make its dissolve, obtain ammonium borate solution, the Mn (NO that is 50wt% by the mass concentration of 0.01～0.03mol 3) 2solution drops in ammonium borate solution, add 10～40mL ethanol, stir 1 hour, be transferred in the polytetrafluoroethylkettle kettle of 60～100mL, stainless steel still shell sealing for polytetrafluoroethylkettle kettle, polytetrafluoroethylkettle kettle is put into the baking oven of 200～220 DEG C, heat 12～24 hours, be cooled to room temperature, carry out suction filtration or centrifuge washing processing, dry 4～6 hours, obtain MnBO for 60～80 DEG C 2oH nano rod bundle presoma;
(2) by MnBO 2oH nano rod bundle presoma is put into resistance furnace, in air atmosphere, is raised to 650～750 DEG C with 5 DEG C/min heating rate, calcines 5～7 hours, naturally cools to room temperature, obtains Mn 2oBO 3nano rod bundle.
CN201410163758.7A 2014-04-22 2014-04-22 A kind of high performance lithium ionic cell cathode material Mn2OBO3Preparation method Active CN103904327B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201410163758.7A CN103904327B (en) 2014-04-22 2014-04-22 A kind of high performance lithium ionic cell cathode material Mn2OBO3Preparation method

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201410163758.7A CN103904327B (en) 2014-04-22 2014-04-22 A kind of high performance lithium ionic cell cathode material Mn2OBO3Preparation method

Publications (2)

Publication Number Publication Date
CN103904327A true CN103904327A (en) 2014-07-02
CN103904327B CN103904327B (en) 2016-05-11

Family

ID=50995551

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201410163758.7A Active CN103904327B (en) 2014-04-22 2014-04-22 A kind of high performance lithium ionic cell cathode material Mn2OBO3Preparation method

Country Status (1)

Country Link
CN (1) CN103904327B (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108023079A (en) * 2017-11-30 2018-05-11 华南理工大学 A kind of hybrid transition metal borate negative material and preparation method thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10209791C1 (en) * 2002-03-01 2003-08-14 Fraunhofer Ges Forschung Anode material used in powder form in a mixture with an electrolyte powder for high temperature fuel cells, or in a gas sensor with an electrolyte powder, comprises a mixed oxide containing rare earth, alkaline earth and transition metals
US20120171571A1 (en) * 2009-06-16 2012-07-05 Sumitomo Chemical Company, Limited Negative electrode material for non-aqueous electrolyte secondary battery and non-aqueous electrolyte secondary battery comprising same
CN102633275A (en) * 2011-02-15 2012-08-15 长春理工大学 Bead chain manganese borate Mn2BO3 one-dimensional nano-fiber and preparation method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10209791C1 (en) * 2002-03-01 2003-08-14 Fraunhofer Ges Forschung Anode material used in powder form in a mixture with an electrolyte powder for high temperature fuel cells, or in a gas sensor with an electrolyte powder, comprises a mixed oxide containing rare earth, alkaline earth and transition metals
US20120171571A1 (en) * 2009-06-16 2012-07-05 Sumitomo Chemical Company, Limited Negative electrode material for non-aqueous electrolyte secondary battery and non-aqueous electrolyte secondary battery comprising same
CN102633275A (en) * 2011-02-15 2012-08-15 长春理工大学 Bead chain manganese borate Mn2BO3 one-dimensional nano-fiber and preparation method thereof

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
B. RIVAS-MURIAS ET AL: "Role of t2g versus e g Interactions in the Physical Properties of A2OBO3(A = Mn, Fe)", 《CHEM. MATER.》 *
I. LEONOV ET AL: "Charge order in Fe2OBO3: An LSDA+U study", 《PHYSICAL REVIEW B》 *
R. NORRESTAM ET AL: "Manganese(II,III) Oxyborate, Mn2OBO3: A Distorted Homometallic Warwickite—Synthesis, Crystal Structure, Band Calculations, and Magnetic Susceptibility", 《JOURNAL OF SOLID STATE CHEMISTRY》 *
唐安平 ET AL: "锂离子电池硼酸盐电极材料的研究进展", 《CHINESE JOURNAL OF APPLIED CHEMISTRY》 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108023079A (en) * 2017-11-30 2018-05-11 华南理工大学 A kind of hybrid transition metal borate negative material and preparation method thereof
CN108023079B (en) * 2017-11-30 2020-05-22 华南理工大学 Mixed transition metal borate anode material and preparation method thereof

Also Published As

Publication number Publication date
CN103904327B (en) 2016-05-11

Similar Documents

Publication Publication Date Title
CN102790217B (en) Carbon cladded ferriferrous oxide negative electrode material of lithium ion battery and preparation method thereof
CN106450195B (en) A kind of positive material for lithium-sulfur battery and preparation method thereof and the lithium-sulfur cell containing the positive electrode
CN103311532B (en) Preparation method of lithium-enriched anode material with nano-grade lamellar-spinel composite structure
CN107275606B (en) Carbon-coated spinel lithium manganate nanocomposite and preparation method and application thereof
CN103872315B (en) A kind of preparation method of cobalt acid lithium composite positive pole of Ge-doped high-energy-density
CN106654245B (en) A kind of preparation method of nanometer tungsten oxide negative electrode material that mixing cobalt
CN108448071B (en) Method for in-situ synthesis of porous nano cobaltosic oxide/carbon negative electrode material
CN106920989B (en) A kind of copper selenium compound is the sodium-ion battery of negative electrode material
CN104241630B (en) Lithium nickel cobalt manganate hollow sphere as well as preparation method and application thereof
CN108183213B (en) Preparation method of ferric oxide/carbon nanotube lithium ion battery cathode material
CN104037412B (en) The preparation method of high performance lithium ion secondary battery negative material multilevel hierarchy nano-hollow ball
CN104409733A (en) Nitrogen doped porous carbon/sulfur composite positive material as well as preparation method and application thereof
CN106910887A (en) A kind of lithium-rich manganese-based anode material, its preparation method and the lithium ion battery comprising the positive electrode
CN104409715A (en) Preparation method of high-performance nitrogen-doped carbon-coated lithium titanate composite anode material of lithium ion battery
CN102838102B (en) Preparation method of lithium iron phosphate monocrystalline nanorods
CN102664255B (en) Lithium nickel manganese oxide material and preparation method thereof, lithium ion battery containing this material
CN104157844A (en) High magnifying power lithium-rich manganese-based cathode material with nano/microstructure
CN105958063A (en) Preparation method of nickel-cobalt-aluminum cathode material used for lithium-ion battery
CN106992295B (en) A kind of preparation method of monodisperse alpha-ferric oxide nanometer sheet
CN103746109A (en) Method for coating lithium ion battery positive pole material lithium manganate by liquid-phase process
CN108598411B (en) Nitrogen-doped carbon-coated tin oxide/iron oxide composite material, preparation method thereof and lithium battery material
CN104617285A (en) Lithium ion battery negative electrode material Li2ZnTi3O8 preparation method
CN107445210B (en) High-capacity iron-based lithium ion battery anode material α -LiFeO2Preparation method of (1)
WO2019104948A1 (en) Molybdenum doping-modified lithium manganese oxide composite material, preparation method therefor and lithium ion battery
CN109244446B (en) Modified nickel-cobalt-manganese ternary cathode 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