CN104934599B - A kind of core shell structure lithium ion battery negative material manganese pyrophosphate and preparation method thereof - Google Patents
A kind of core shell structure lithium ion battery negative material manganese pyrophosphate and preparation method thereof Download PDFInfo
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- CN104934599B CN104934599B CN201510200353.0A CN201510200353A CN104934599B CN 104934599 B CN104934599 B CN 104934599B CN 201510200353 A CN201510200353 A CN 201510200353A CN 104934599 B CN104934599 B CN 104934599B
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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
- H01M4/58—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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- 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
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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
- 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
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
A kind of core shell structure lithium ion battery negative material manganese pyrophosphate and preparation method thereof, the manganese pyrophosphate is made in accordance with the following methods：（1）Organic Mn source and phosphorus source are dissolved in deionized water, mixed solution is obtained；（2）Adjust pH value to 3~8；（3）It is placed in 60~90 DEG C of water-baths, stirs 10~30h, forms homogeneous gel；（4）At 60~110 DEG C, 4~15h is dried, obtain manganese pyrophosphate presoma；（5）It is placed in non-oxidizing atmosphere, at 350~700 DEG C, sinters 4~14h, be cooled to room temperature, obtains core shell structure lithium ion battery negative material manganese pyrophosphate.The nanometer rods of manganese pyrophosphate of the present invention are core shell structure, with specific surface area higher, be conducive to the infiltration of the transmission and electrolyte of ion to electrode material, and the amorphous carbon that nanometer rods outer layer is uniformly coated can greatly improve its electric conductivity, and material electrochemical performance is excellent.
Description
Technical field
The present invention relates to a kind of lithium ion battery negative material and preparation method thereof, and in particular to a kind of core shell structure lithium from
Sub- cell negative electrode material manganese pyrophosphate and preparation method thereof.
Background technology
The energy density of lithium ion battery depends primarily on output voltage and specific capacity, and these again rely on electrode material
Chemical property, one of key of the preferable lithium ion battery of exploitation is exactly to find suitable electrolysis material, wherein, negative material
It is again the critical material of li-ion electrode materials.Exploitation low-voltage, high power capacity, long-life, the negative material of safety and stability are many
The most important thing of many researcher's concerns.Conventional graphite negative pole is relatively low due to capacity（It is 372mAh/g）And limit lithium ion battery
To high power capacity evolution of objective, novel graphite alkene limits its expansion and uses because its preparation technology is difficult, expensive, closes
Volumetric expansion during removal lithium embedded is big and influence high rate performance due to it for gold and metal oxide, therefore, exploitation novel lithium from
Sub- cell negative electrode material seems very necessary.
In polyanion inorganic salt materials, manganese pyrophosphate（Mn2P2O7）Due to its there are the active sites of lithium ion deintercalation and
Can be as lithium ion battery negative material.But, there is no report that synthesized manganese pyrophosphate is applied to lithium-ion electric at present
Pond negative material.CN103539098A discloses a kind of method for preparing manganese pyrophosphate nanometer sheet, according to Jiao prepared by its method
When manganese phosphate nanometer sheet is used for lithium ion battery, due to the Mn disproportionated reactions in the electrolytic solution in charge and discharge process, it may occur that
The dissolving of Mn, causes material electrochemical performance to decline, and nanometer sheet pattern considerably increases work due to its excessive specific surface area
Property material and electrolyte contact area, therefore, nanometer sheet manganese pyrophosphate can promote the dissolving of Mn, and the electric conductivity of manganese pyrophosphate is not
It is good, the chemical property of material can be influenceed during as lithium ion battery electrode material.
CN104091953A discloses a kind of lithium ion battery negative material pyrophosphoric acid vanadium and preparation method thereof, in its raw material
Reducing agent must be used, the pattern of the final product for obtaining is nano-sheet, and without carbon coated so that its electric conductivity is not good enough.
The content of the invention
The technical problems to be solved by the invention are to provide a kind of with specific surface area higher, electrochemical performance
Core shell structure lithium ion battery negative material manganese pyrophosphate and preparation method thereof.
The technical solution adopted for the present invention to solve the technical problems is as follows：A kind of core shell structure lithium ion battery negative material
Material manganese pyrophosphate, is made in accordance with the following methods：
（1）It is 1 according to the mol ratio of P elements in manganese element in Organic Mn source and phosphorus source by Organic Mn source and phosphorus source:1
Ratio, is dissolved in deionized water, obtains mixed solution；
（2）By step（1）Gained mixed solution adjusts pH value to 3~8；
（3）By step（2）Mixed solution after regulation pH value is placed in 60~90 DEG C of water-baths, stirs 10~30h, forms equal
One gel；
（4）By step（3）Gained gel dries 4~15h at 60~110 DEG C, obtains manganese pyrophosphate presoma；
（5）By step（4）Gained manganese pyrophosphate presoma is placed in non-oxidizing atmosphere, at 350~700 DEG C, sinters 4
~14h, is cooled to room temperature, obtains final product core shell structure lithium ion battery negative material manganese pyrophosphate.
Further, step（1）In, the concentration of manganese ion is controlled in 0.04~0.2mol/L in the mixed solution.Manganese from
Sub- concentration control is more beneficial for obtaining the material of nanoscale core shell structure in the scope.
Further, step（4）In, the dry temperature is 80~100 DEG C, and the dry time is 5~12h.
Further, step（5）In, the temperature of the sintering is 400~650 DEG C, and the time of sintering is 6~12h.
Further, step（5）In, the non-oxidizing atmosphere is in argon gas, nitrogen, helium, hydrogen or carbon monoxide
One or more.
Further, step（1）In, the Organic Mn source is disodium ethylene diamine tetraacetate manganese and/or manganese acetylacetonate.
Further, step（1）In, phosphorus source is ammonium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium phosphate, phosphoric acid or pyrophosphoric acid
In one or more.
The present invention, as raw material, manganese pyrophosphate is prepared by " sol-gel " using Organic Mn source, brilliant using manganese pyrophosphate
The preferential growth in face, and nano bar-shape material precursor is prepared, in sintering process, Organic Mn source is produced by Pintsch process
Carbon, on the one hand can serve as reducing agent in chemical reaction, it is to avoid the use of reducing agent, on the other hand because carbon and manganese are all originated
In same Organic Mn source compound, carbon can form the melting carbon of cracking during Pintsch process, the melting carbon of cracking due to
It is that liquid condition can be coated on prepared manganese pyrophosphate nanometer rods outer layer to outflow, carbon coating in situ is carried out to nanometer rods,
So as to prepare the nanometer rods manganese pyrophosphate with core shell structure, because the conductance of carbon is higher, the cladding for cracking carbon can be improved
The electric conductivity of manganese pyrophosphate nanometer rods.The nanometer rods of core shell structure can improve material electrochemical performance, and nano material can be lithium
Ion provides its more embedding lithium avtive spot, shorter diffusion path, to improve its transmission rate；Shorter mass transfer, load transfer
Distance and larger specific surface area fully infiltrate for electrolyte with active material, are finally improved the conduction of electrode material
Property.Mn2P2O7In P2O7 4-It is by two PO4 3-Cross-linked polymeric is formed, with sufficiently stable three-dimensional frame structure, therefore, tool
There are unobstructed lithium ion deintercalation passage, the structure and reliable security of stabilization, be a kind of novel cathode material for lithium ion battery.
In Mn2P2O7The amorphous carbon that outside is evenly coated further increases the chemical property of material.
The preparation method synthesis temperature of manganese pyrophosphate of the present invention is low, and the reaction time is short, and step is simple, and raw material is easy to get, and is easy to
Industrialization, has prepared the Mn of core shell structure first2P2O7Material, its microscopic appearance is the nanometer rods of uniform core shell structure, is
It is inner core by constitutionally stable manganese pyrophosphate, the carbon-coating of non-crystalline is the core shell structure of housing combination, and product is once
Particle diameter can be effectively controlled between 100~500nm, and nano bar-shape material has specific surface area higher, is conducive to electrolyte pair
The abundant infiltration of material, and the path of ion transmission is substantially reduced, be conducive to the transmission of ion and electronics, outside uniform bag
The amorphous state carbon-coating for covering can greatly promote the electronic conductivity of material, further improve the chemical property of material, by it
Button cell is assembled into, 0.1C first discharge specific capacities are up to 645.4mAh/g, and 0.5C first discharge specific capacities are reachable
, up to 506.7mAh/g, specific discharge capacity can after circulating 100 times under 0.1C multiplying powers for 589.4mAh/g, 1C first discharge specific capacity
Up to 517.5mAh/g.The special microscopic appearance is to negative material Mn2P2O7The chemical property effect of having greatly improved, performance
Go out excellent chemical property.
Brief description of the drawings
Fig. 1 is the XRD of the lithium ion battery negative material manganese pyrophosphate obtained by the embodiment of the present invention 2；
Fig. 2 is the SEM figures of the lithium ion battery negative material manganese pyrophosphate obtained by the embodiment of the present invention 2；
Fig. 3 is the TEM figures of the lithium ion battery negative material manganese pyrophosphate obtained by the embodiment of the present invention 2.
Specific embodiment
With reference to embodiment and accompanying drawing, the invention will be further described.
Reagent used by embodiment of the present invention regulation pH value is the ammoniacal liquor and molar concentration of 25~28wt% of mass concentration
The hydrochloric acid of 0.5mol/L；Other chemical reagent for being used, unless otherwise specified, are obtained by routine business approach.
Embodiment 1
（1）0.005mol disodium ethylene diamine tetraacetates manganese and 0.005mol ammonium dihydrogen phosphates are mixed, and is dissolved in 100mL
Deionized water in, obtain mixed solution；
（2）By step（1）Gained mixed solution adjusts pH value to 3；
（3）By step（2）Mixed solution after regulation pH value is placed in 60 DEG C of thermostat water baths, and mechanical agitation 30h is formed
Homogeneous gel；
（4）By step（3）Gained gel, at 60 DEG C, dries 15h in vacuum drying chamber, obtains manganese pyrophosphate presoma；
（5）By step（4）Gained manganese pyrophosphate presoma is placed in pipe type sintering furnace, under an argon atmosphere, in 700 DEG C of burnings
Knot 12h, naturally cools to room temperature, obtains final product core shell structure lithium ion battery negative material manganese pyrophosphate.
After testing, gained core shell structure lithium ion battery negative material manganese pyrophosphate is in nano bar-shape, and its average grain diameter is
500nm。
By gained core shell structure Mn2P2O7Nanometer rods, are assembled into the button cell of CR2025, by battery in 0.01V~1.5V
Its charge/discharge capacity and high rate performance are surveyed in voltage range, wherein, 0.1C first discharge specific capacities are 445.4mAh/g, and 0.5C is first
Secondary specific discharge capacity is 378.4mAh/g, and 1C first discharge specific capacities are 316.4mAh/g, after circulating 100 times under 0.1C multiplying powers
Specific discharge capacity is 307.3mAh/g.
Embodiment 2
（1）0.008mol manganese acetylacetonates and 0.008mol diammonium hydrogen phosphates are mixed, and is dissolved in the deionization of 100mL
In water, mixed solution is obtained；
（2）By step（1）Gained mixed solution adjusts pH value to 7；
（3）By step（2）Mixed solution after regulation pH value is placed in 80 DEG C of thermostat water baths, and mechanical agitation 15h is formed
Homogeneous gel；
（4）By step（3）Gained gel, at 100 DEG C, dries 5h in vacuum drying oven, obtains manganese pyrophosphate presoma；
（5）By step（4）Gained manganese pyrophosphate presoma is placed in pipe type sintering furnace, in a nitrogen atmosphere, in 600 DEG C of burnings
Knot 8h, naturally cools to room temperature, obtains final product core shell structure lithium ion battery plus-negative plate material manganese pyrophosphate.
After testing, gained core shell structure lithium ion battery negative material manganese pyrophosphate is in nano bar-shape, and its average grain diameter is
100nm；The XRD of the core shell structure manganese pyrophosphate nanometer rods is as shown in figure 1, the Mn of pure phase has been prepared in explanation2P2O7；SEM
Figure is as shown in Fig. 2 TEM figures are as shown in figure 3, from Fig. 2,3, prepared Mn2P2O7Microscopic appearance be uniform core shell knot
Structure nanometer rods.
By gained core shell structure Mn2P2O7Nanometer rods, are assembled into the button cell of CR2025, by battery in 0.01V~1.5V
Its charge/discharge capacity and high rate performance are surveyed in voltage range, wherein, 0.1C first discharge specific capacities are 645.4mAh/g, and 0.5C is first
Secondary specific discharge capacity is 589.4mAh/g, and 1C first discharge specific capacities are 506.7mAh/g, after circulating 100 times under 0.1C multiplying powers
Specific discharge capacity is 517.5mAh/g.
Embodiment 3
（1）0.05mol disodium ethylene diamine tetraacetates manganese and 0.05mol ammonium phosphate are mixed, and is dissolved in going for 1000mL
In ionized water, mixed solution is obtained；
（2）By step（1）Gained mixed solution adjusts pH value to 5；
（3）By step（2）Mixed solution after regulation pH value is placed in 90 DEG C of thermostat water baths, and mechanical agitation 10h is formed
Homogeneous gel；
（4）By step（3）Gained gel is placed in vacuum drying oven at 80 DEG C, dries 12h, obtains manganese pyrophosphate presoma；
（5）By step（4）Gained manganese pyrophosphate presoma is placed in pipe type sintering furnace, under an argon atmosphere, in 400 DEG C of burnings
Knot 12h, naturally cools to room temperature, obtains final product core shell structure lithium ion battery negative material manganese pyrophosphate.
After testing, gained core shell structure lithium ion battery negative material manganese pyrophosphate is in nano bar-shape, and its average grain diameter is
150nm。
By gained core shell structure Mn2P2O7Nanometer rods, are assembled into the button cell of CR2025, by battery in 0.01V~1.5V
Its charge/discharge capacity and high rate performance are surveyed in voltage range, wherein 0.1C first discharge specific capacities are 545.4mAh/g, and 0.5C is first
Secondary specific discharge capacity is 478.4mAh/g, and 1C first discharge specific capacities are 416.4mAh/g, after circulating 100 times under 0.1C multiplying powers
Specific discharge capacity is 407.3mAh/g.
Embodiment 4
（1）0.04mol manganese acetylacetonates and 0.04mol diammonium hydrogen phosphates are mixed, and is dissolved in the deionized water of 200mL
In, obtain mixed solution；
（2）By step（1）Gained mixed solution adjusts pH value to 8；
（3）By step（2）Mixed solution after regulation pH value is placed in 80 DEG C of thermostat water baths, and mechanical agitation 20h is formed
Homogeneous gel；
（4）By step（3）Gained gel is placed in vacuum drying oven at 90 DEG C, dries 10h, obtains manganese pyrophosphate presoma；
（5）By step（4）Gained manganese pyrophosphate presoma is placed in pipe type sintering furnace, under an argon atmosphere, in 650 DEG C of burnings
Knot 4h, naturally cools to room temperature, obtains final product core shell structure lithium ion battery negative material manganese pyrophosphate.
After testing, gained core shell structure lithium ion battery negative material manganese pyrophosphate is in nano bar-shape, and its average grain diameter is
200nm。
By gained core shell structure Mn2P2O7Nanometer rods, are assembled into the button cell of CR2025, by battery in 0.01V~1.5V
Its charge/discharge capacity and high rate performance are surveyed in voltage range, wherein 0.1C first discharge specific capacities are 485.4mAh/g, and 0.5C is first
Secondary specific discharge capacity is 408.5mAh/g, and 1C first discharge specific capacities are 376.7mAh/g, after circulating 100 times under 0.1C multiplying powers
Specific discharge capacity is 327.3mAh/g.
Embodiment 5
（1）0.06mol manganese acetylacetonates and 0.06mol phosphoric acid are mixed, and is dissolved in the deionized water of 1000mL, obtained
Mixed solution；
（2）By step（1）Gained mixed solution adjusts pH value to 7；
（3）By step（2）Mixed solution after regulation pH value is placed in 80 DEG C of thermostat water baths, and mechanical agitation 24h is formed
Homogeneous gel；
（4）By step（3）Gained gel is placed in vacuum drying oven at 90 DEG C, dries 5h, obtains manganese pyrophosphate presoma；
（5）By step（4）Gained manganese pyrophosphate presoma is placed in pipe type sintering furnace, under an argon atmosphere, in 700 DEG C of burnings
Knot 8h, naturally cools to room temperature, obtains final product core shell structure lithium ion battery negative material manganese pyrophosphate.
After testing, gained core shell structure lithium ion battery negative material manganese pyrophosphate is in nano bar-shape, and its average grain diameter is
350nm。
By gained core shell structure Mn2P2O7Nanometer rods, are assembled into the button cell of CR2025, by battery in 0.01V~1.5V
Its charge/discharge capacity and high rate performance are surveyed in voltage range, wherein 0.1C first discharge specific capacities are 405.7mAh/g, and 0.5C is first
Secondary specific discharge capacity is 358.4mAh/g, and 1C first discharge specific capacities are 326.4mAh/g, after circulating 100 times under 0.1C multiplying powers
Specific discharge capacity is 317.3mAh/g.
Claims (7)
1. a kind of core shell structure lithium ion battery negative material manganese pyrophosphate, it is characterised in that be made in accordance with the following methods：
（1）It is 1 according to the mol ratio of P elements in manganese element in Organic Mn source and phosphorus source by Organic Mn source and phosphorus source:1 ratio,
It is dissolved in deionized water, obtains mixed solution；The Organic Mn source is disodium ethylene diamine tetraacetate manganese and/or manganese acetylacetonate；Institute
The concentration for stating manganese ion in mixed solution is controlled in 0.04~0.2mol/L；
（2）By step（1）Gained mixed solution adjusts pH value to 3~8；
（3）By step（2）Mixed solution after regulation pH value is placed in 60~90 DEG C of water-baths, stirs 10~30h, forms homogeneous solidifying
Glue；
（4）By step（3）Gained gel dries 4~15h at 60~110 DEG C, obtains manganese pyrophosphate presoma；
（5）By step（4）Gained manganese pyrophosphate presoma is placed in non-oxidizing atmosphere, at 350~700 DEG C, sintering 4~
14h, is cooled to room temperature, obtains final product core shell structure lithium ion battery negative material manganese pyrophosphate.
2. core shell structure lithium ion battery negative material manganese pyrophosphate according to claim 1, it is characterised in that：Step（4）
In, the dry temperature is 80~100 DEG C, and the dry time is 5~12h.
3. core shell structure lithium ion battery negative material manganese pyrophosphate according to claim 1 or claim 2, it is characterised in that：Step
（5）In, the temperature of the sintering is 400~650 DEG C, and the time of sintering is 6~12h.
4. core shell structure lithium ion battery negative material manganese pyrophosphate according to claim 1 or claim 2, it is characterised in that：Step
（5）In, the non-oxidizing atmosphere is one or more in argon gas, nitrogen, helium, hydrogen or carbon monoxide.
5. core shell structure lithium ion battery negative material manganese pyrophosphate according to claim 1 or claim 2, it is characterised in that：Step
（1）In, phosphorus source is one or more in ammonium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium phosphate, phosphoric acid or pyrophosphoric acid.
6. core shell structure lithium ion battery negative material manganese pyrophosphate according to claim 3, it is characterised in that：Step（1）
In, phosphorus source is one or more in ammonium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium phosphate, phosphoric acid or pyrophosphoric acid.
7. core shell structure lithium ion battery negative material manganese pyrophosphate according to claim 4, it is characterised in that：Step（1）
In, phosphorus source is one or more in ammonium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium phosphate, phosphoric acid or pyrophosphoric acid.
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| CN107697895B (en) * | 2017-09-13 | 2019-11-15 | 宁波致良新能源有限公司 | A kind of nanoporous manganese pyrophosphate and preparation method thereof |
| CN110098383B (en) * | 2018-01-29 | 2021-06-22 | 宁德新能源科技有限公司 | Cathode material, preparation method thereof, battery cathode and lithium ion battery |
| CN109853085B (en) * | 2018-12-13 | 2021-08-06 | 大连理工大学 | Regulating and controlling method for conductivity of composite nanofiber with amorphous carbon-reductive graphene oxide-cobaltosic oxide coating structure |
| CN110217771A (en) * | 2019-05-21 | 2019-09-10 | 中南大学 | A kind of manganese pyrophosphate polyanionic lithium cell cathode material and preparation method thereof |
| CN110589789B (en) * | 2019-09-07 | 2023-02-17 | 中南大学 | Preparation method of negative electrode material nano needle-shaped antimony phosphate |
| CN111900382B (en) * | 2020-07-21 | 2021-06-15 | 多助科技(武汉)有限公司 | Preparation method and application of manganese pyrophosphate electrode material |
| CN113036101A (en) * | 2021-02-26 | 2021-06-25 | 中国科学院宁波材料技术与工程研究所 | Carbon-coated pyrophosphate and preparation method and application thereof |
| CN113877611B (en) * | 2021-09-26 | 2023-10-31 | 安徽工业大学 | Phosphoric acid modified manganese oxide supported catalyst and preparation method thereof |
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| CN104091953A (en) * | 2014-07-30 | 2014-10-08 | 中南大学 | Lithium ion battery negative material-vanadium pyrophosphate and preparation method thereof |
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