CN104934599A - Mn2P2O7 anode material of core-shell structured lithium ion battery and preparation method thereof - Google Patents
Mn2P2O7 anode material of core-shell structured lithium ion battery and preparation method thereof Download PDFInfo
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- CN104934599A CN104934599A CN201510200353.0A CN201510200353A CN104934599A CN 104934599 A CN104934599 A CN 104934599A CN 201510200353 A CN201510200353 A CN 201510200353A CN 104934599 A CN104934599 A CN 104934599A
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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
The invention relates to a Mn2P2O7 anode material of a core-shell structured lithium ion battery and a preparation method thereof. The Mn2P2O7 is prepared according to the following steps of: (1) dissolving an organic manganese source and a phosphorus source in deionized water to obtain a mixed solution; (2) adjusting a pH value to be 3 to 8; (3) placing the solution in a water bath at 60 to 90 DEG C, and stirring the solution for 10 to 30 hours to form uniform gel; (4) drying the gel for 4 to 15 hours at 60 to 110 DEG C to obtain a Mn2P2O7 precursor; and (5) placing the Mn2P2O7 precursor in a non-oxidizing atmosphere, sintering the Mn2P2O7 precursor at 350 to 700 DEG C for 4 to 14 hours, and cooling the product to the room temperature, thereby obtaining the Mn2P2O7 anode material of the core-shell structured lithium ion battery. The nanometer rod of the Mn2P2O7 is of a core-shell structure and has high specific area, thereby being favorable for ion transmission and infiltration of an electrolyte to an electrode material; and moreover, the conductivity of the nanometer rod is greatly improved due to uniformly-coated amorphous carbon, and the electrochemical performance of the material is excellent.
Description
Technical field
The present invention relates to a kind of lithium ion battery cathode material and its preparation method, be specifically related to a kind of core shell structure lithium ion battery negative 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 depend on the chemical property of electrode material, developing one of key of desirable lithium ion battery is exactly find suitable electrolysis material, and wherein, negative material is again the critical material of li-ion electrode materials.The negative material of exploitation low-voltage, high power capacity, long-life, safety and stability is the most important thing that numerous researcher pays close attention to.Conventional graphite negative pole limits lithium ion battery to high power capacity evolution of objective due to capacity lower (for 372mAh/g), novel graphite alkene limits it and expands use because its preparation technology is difficult, expensive, alloy and metal oxide affect high rate performance because its volumetric expansion in removal lithium embedded process is large, therefore, development of new lithium ion battery negative material seems very necessary.
In polyanion inorganic salt materials, manganese pyrophosphate (Mn
2p
2o
7) due to its have lithium ion deintercalation active sites and can as lithium ion battery negative material.But, there is no report at present and synthesized manganese pyrophosphate be applied to lithium ion battery negative material.CN103539098A discloses a kind of method preparing manganese pyrophosphate nanometer sheet, when the manganese pyrophosphate nanometer sheet prepared according to its method is for lithium ion battery, due to Mn disproportionated reaction in the electrolytic solution in charge and discharge process, the dissolving of Mn can be there is, material electrochemical performance is caused to decline, and nanometer sheet pattern considerably increases the contact area of active material and electrolyte due to its excessive specific area, therefore, nanometer sheet manganese pyrophosphate can impel the dissolving of Mn, the conductivity of manganese pyrophosphate is not good, as the chemical property that can affect material during lithium ion battery electrode material.
CN104091953A discloses a kind of lithium ion battery negative material pyrophosphoric acid vanadium and preparation method thereof, must use reducing agent in its raw material, and the pattern of the final product obtained is nano-sheet, and does not have carbon coated, makes its conductivity not good enough.
Summary of the invention
Technical problem to be solved by this invention is, provides a kind of and has higher specific area, core shell structure lithium ion battery negative material manganese pyrophosphate of electrochemical performance 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 manganese pyrophosphate, makes in accordance with the following methods:
(1) be the ratio of 1:1 by Organic Mn source and phosphorus source according to the mol ratio of P elements in manganese element in Organic Mn source and phosphorus source, be dissolved in deionized water, obtain mixed solution;
(2) by step (1) gained mixed solution adjust ph to 3 ~ 8;
(3) mixed solution after step (2) adjust ph is placed in 60 ~ 90 DEG C of water-baths, stirs 10 ~ 30h, form homogeneous gel;
(4) by step (3) gained gel at 60 ~ 110 DEG C, dry 4 ~ 15h, obtains manganese pyrophosphate presoma;
(5) 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 core shell structure lithium ion battery negative material manganese pyrophosphate.
Further, in step (1), in described mixed solution, the concentration of manganese ion controls at 0.04 ~ 0.2mol/L.Manganese ion concentration controls the material being more conducive to obtaining nanoscale core shell structure in this scope.
Further, in step (4), the temperature of described drying is 80 ~ 100 DEG C, and the dry time is 5 ~ 12h.
Further, in step (5), the temperature of described sintering is 400 ~ 650 DEG C, and the time of sintering is 6 ~ 12h.
Further, in step (5), described non-oxidizing atmosphere is one or more in argon gas, nitrogen, helium, hydrogen or carbon monoxide.
Further, in step (1), described Organic Mn source is disodium ethylene diamine tetraacetate manganese and/or manganese acetylacetonate.
Further, in step (1), described phosphorus source is one or more in ammonium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium phosphate, phosphoric acid or pyrophosphoric acid.
The present invention adopts Organic Mn source as raw material, manganese pyrophosphate is prepared by " sol-gel ", utilize the preferential growth of manganese pyrophosphate crystal face, and prepare nano bar-shape material precursor, in sintering process, Organic Mn source produces carbon by Pintsch process, reducing agent can be served as on the one hand in chemical reaction, avoid the use of reducing agent, on the other hand because carbon and manganese all derive from same Organic Mn source compound, carbon can form the melting carbon of cracking in Pintsch process process, the melting carbon of cracking is owing to being that liquid condition can to outflow, be coated on prepared manganese pyrophosphate nanometer rods outer, in-situ carbon carried out to nanometer rods coated, thus prepare the nanometer rods manganese pyrophosphate with core shell structure, because the conductance of carbon is higher, the coated conductivity that can improve manganese pyrophosphate nanometer rods of cracking carbon.The nanometer rods of core shell structure can improve material electrochemical performance, embedding lithium avtive spot, shorter the evolving path that nano material can provide it more for lithium ion, to improve its transmission rate; The specific area that shorter mass transfer, load transfer Distance geometry are larger fully infiltrates for electrolyte and active material, is finally improved the conductivity of electrode material.Mn
2p
2o
7in P
2o
7 4-by two PO
4 3-cross-linked polymeric forms, and has very stable three-dimensional frame structure, and therefore, having unobstructed lithium ion deintercalation passage, stable structure and fail safe reliably, is a kind of Novel cathode material for lithium ion battery.At Mn
2p
2o
7outside coated uniform amorphous carbon further increases the chemical property of material.
Preparation method's 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 convenient to industrialization, has prepared the Mn of core shell structure first
2p
2o
7material, its microscopic appearance is the nanometer rods of uniform core shell structure, be inner core by constitutionally stable manganese pyrophosphate, the carbon-coating of non-crystalline is the core shell structure of housing combination, the primary particle size of product can effectively control between 100 ~ 500nm, nano bar-shape material has higher specific area, be conducive to the abundant infiltration of electrolyte to material, and substantially reduce the path of ion transfer, be conducive to the transmission of ion and electronics, outside evenly coated amorphous state carbon-coating can promote the electronic conductivity of material greatly, improve the chemical property of material further, be assembled into button cell, 0.1C first discharge specific capacity can reach 645.4mAh/g, 0.5C first discharge specific capacity can reach 589.4mAh/g, 1C first discharge specific capacity can reach 506.7mAh/g, the specific discharge capacity after 100 times that circulates under 0.1C multiplying power can reach 517.5mAh/g.This special microscopic appearance anticathode material Mn
2p
2o
7the chemical property effect of having greatly improved, show excellent chemical property.
Accompanying drawing explanation
Fig. 1 is the XRD figure of the lithium ion battery negative material manganese pyrophosphate obtained by the embodiment of the present invention 2;
Fig. 2 is the SEM figure of the lithium ion battery negative material manganese pyrophosphate obtained by the embodiment of the present invention 2;
Fig. 3 is the TEM figure of the lithium ion battery negative material manganese pyrophosphate obtained by the embodiment of the present invention 2.
Embodiment
Below in conjunction with embodiment and accompanying drawing, the invention will be further described.
Embodiment of the present invention adjust ph reagent used is the ammoniacal liquor of mass concentration 25 ~ 28wt% and the hydrochloric acid of molar concentration 0.5mol/L; Other chemical reagent used, if no special instructions, is all obtained by routine business approach.
embodiment 1
(1) by 0.005mol disodium ethylene diamine tetraacetate manganese and the mixing of 0.005mol ammonium dihydrogen phosphate, and be dissolved in the deionized water of 100mL, obtain mixed solution;
(2) by step (1) gained mixed solution adjust ph to 3;
(3) mixed solution after step (2) adjust ph is placed in 60 DEG C of thermostat water baths, mechanical agitation 30h, forms homogeneous gel;
(4) by step (3) gained gel in vacuum drying chamber at 60 DEG C, dry 15h, obtains manganese pyrophosphate presoma;
(5) step (4) gained manganese pyrophosphate presoma is placed in pipe type sintering furnace, under an argon atmosphere, in 700 DEG C of sintering 12h, naturally cools to room temperature, obtain core shell structure lithium ion battery negative material manganese pyrophosphate.
After testing, gained core shell structure lithium ion battery negative material manganese pyrophosphate is nano bar-shape, and its average grain diameter is 500nm.
By gained core shell structure Mn
2p
2o
7nanometer rods, be assembled into the button cell of CR2025, battery is surveyed its charge/discharge capacity and high rate performance in 0.01V ~ 1.5V voltage range, wherein, 0.1C first discharge specific capacity is 445.4mAh/g, 0.5C first discharge specific capacity is 378.4mAh/g, 1C first discharge specific capacity is 316.4mAh/g, and the specific discharge capacity after 100 times that circulates under 0.1C multiplying power is 307.3mAh/g.
embodiment 2
(1) by 0.008mol manganese acetylacetonate and the mixing of 0.008mol diammonium hydrogen phosphate, and be dissolved in the deionized water of 100mL, obtain mixed solution;
(2) by step (1) gained mixed solution adjust ph to 7;
(3) mixed solution after step (2) adjust ph is placed in 80 DEG C of thermostat water baths, mechanical agitation 15h, forms homogeneous gel;
(4) by step (3) gained gel in vacuum drying oven at 100 DEG C, dry 5h, obtains manganese pyrophosphate presoma;
(5) step (4) gained manganese pyrophosphate presoma is placed in pipe type sintering furnace, in a nitrogen atmosphere, in 600 DEG C of sintering 8h, naturally cools to room temperature, obtain 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 nano bar-shape, and its average grain diameter is 100nm; The XRD figure of described core shell structure manganese pyrophosphate nanometer rods as shown in Figure 1, illustrates the Mn having prepared pure phase
2p
2o
7; As shown in Figure 2, TEM schemes as shown in Figure 3 SEM figure, from Fig. 2,3, and prepared Mn
2p
2o
7microscopic appearance be uniform core shell structure nanometer rods.
By gained core shell structure Mn
2p
2o
7nanometer rods, be assembled into the button cell of CR2025, battery is surveyed its charge/discharge capacity and high rate performance in 0.01V ~ 1.5V voltage range, wherein, 0.1C first discharge specific capacity is 645.4mAh/g, 0.5C first discharge specific capacity is 589.4mAh/g, 1C first discharge specific capacity is 506.7mAh/g, and the specific discharge capacity after 100 times that circulates under 0.1C multiplying power is 517.5mAh/g.
embodiment 3
(1) by 0.05mol disodium ethylene diamine tetraacetate manganese and the mixing of 0.05mol ammonium phosphate, and be dissolved in the deionized water of 1000mL, obtain mixed solution;
(2) by step (1) gained mixed solution adjust ph to 5;
(3) mixed solution after step (2) adjust ph is placed in 90 DEG C of thermostat water baths, mechanical agitation 10h, forms homogeneous gel;
(4) be placed in by step (3) gained gel in vacuum drying oven at 80 DEG C, dry 12h, obtains manganese pyrophosphate presoma;
(5) step (4) gained manganese pyrophosphate presoma is placed in pipe type sintering furnace, under an argon atmosphere, in 400 DEG C of sintering 12h, naturally cools to room temperature, obtain core shell structure lithium ion battery negative material manganese pyrophosphate.
After testing, gained core shell structure lithium ion battery negative material manganese pyrophosphate is nano bar-shape, and its average grain diameter is 150nm.
By gained core shell structure Mn
2p
2o
7nanometer rods, be assembled into the button cell of CR2025, battery is surveyed its charge/discharge capacity and high rate performance in 0.01V ~ 1.5V voltage range, wherein 0.1C first discharge specific capacity is 545.4mAh/g, 0.5C first discharge specific capacity is 478.4mAh/g, 1C first discharge specific capacity is 416.4mAh/g, and the specific discharge capacity after 100 times that circulates under 0.1C multiplying power is 407.3mAh/g.
embodiment 4
(1) by 0.04mol manganese acetylacetonate and the mixing of 0.04mol diammonium hydrogen phosphate, and be dissolved in the deionized water of 200mL, obtain mixed solution;
(2) by step (1) gained mixed solution adjust ph to 8;
(3) mixed solution after step (2) adjust ph is placed in 80 DEG C of thermostat water baths, mechanical agitation 20h, forms homogeneous gel;
(4) be placed in by step (3) gained gel in vacuum drying oven at 90 DEG C, dry 10h, obtains manganese pyrophosphate presoma;
(5) step (4) gained manganese pyrophosphate presoma is placed in pipe type sintering furnace, under an argon atmosphere, in 650 DEG C of sintering 4h, naturally cools to room temperature, obtain core shell structure lithium ion battery negative material manganese pyrophosphate.
After testing, gained core shell structure lithium ion battery negative material manganese pyrophosphate is nano bar-shape, and its average grain diameter is 200nm.
By gained core shell structure Mn
2p
2o
7nanometer rods, be assembled into the button cell of CR2025, battery is surveyed its charge/discharge capacity and high rate performance in 0.01V ~ 1.5V voltage range, wherein 0.1C first discharge specific capacity is 485.4mAh/g, 0.5C first discharge specific capacity is 408.5mAh/g, 1C first discharge specific capacity is 376.7mAh/g, and the specific discharge capacity after 100 times that circulates under 0.1C multiplying power is 327.3mAh/g.
embodiment 5
(1) by 0.06mol manganese acetylacetonate and the mixing of 0.06mol phosphoric acid, and be dissolved in the deionized water of 1000mL, obtain mixed solution;
(2) by step (1) gained mixed solution adjust ph to 7;
(3) mixed solution after step (2) adjust ph is placed in 80 DEG C of thermostat water baths, mechanical agitation 24h, forms homogeneous gel;
(4) be placed in by step (3) gained gel in vacuum drying oven at 90 DEG C, dry 5h, obtains manganese pyrophosphate presoma;
(5) step (4) gained manganese pyrophosphate presoma is placed in pipe type sintering furnace, under an argon atmosphere, in 700 DEG C of sintering 8h, naturally cools to room temperature, obtain core shell structure lithium ion battery negative material manganese pyrophosphate.
After testing, gained core shell structure lithium ion battery negative material manganese pyrophosphate is nano bar-shape, and its average grain diameter is 350nm.
By gained core shell structure Mn
2p
2o
7nanometer rods, be assembled into the button cell of CR2025, battery is surveyed its charge/discharge capacity and high rate performance in 0.01V ~ 1.5V voltage range, wherein 0.1C first discharge specific capacity is 405.7mAh/g, 0.5C first discharge specific capacity is 358.4mAh/g, 1C first discharge specific capacity is 326.4mAh/g, and the specific discharge capacity after 100 times that circulates under 0.1C multiplying power is 317.3mAh/g.
Claims (10)
1. a core shell structure lithium ion battery negative material manganese pyrophosphate, is characterized in that, makes in accordance with the following methods:
(1) be the ratio of 1:1 by Organic Mn source and phosphorus source according to the mol ratio of P elements in manganese element in Organic Mn source and phosphorus source, be dissolved in deionized water, obtain mixed solution;
(2) by step (1) gained mixed solution adjust ph to 3 ~ 8;
(3) mixed solution after step (2) adjust ph is placed in 60 ~ 90 DEG C of water-baths, stirs 10 ~ 30h, form homogeneous gel;
(4) by step (3) gained gel at 60 ~ 110 DEG C, dry 4 ~ 15h, obtains manganese pyrophosphate presoma;
(5) 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 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, is characterized in that: in step (1), in described mixed solution, the concentration of manganese ion controls at 0.04 ~ 0.2mol/L.
3. core shell structure lithium ion battery negative material manganese pyrophosphate according to claim 1 or 2, is characterized in that: in step (4), the temperature of described drying is 80 ~ 100 DEG C, and the dry time is 5 ~ 12h.
4. core shell structure lithium ion battery negative material manganese pyrophosphate according to claim 1 or 2, it is characterized in that: in step (5), the temperature of described sintering is 400 ~ 650 DEG C, the time of sintering is 6 ~ 12h.
5. core shell structure lithium ion battery negative material manganese pyrophosphate according to claim 3, it is characterized in that: in step (5), the temperature of described sintering is 400 ~ 650 DEG C, and the time of sintering is 6 ~ 12h.
6. core shell structure lithium ion battery negative material manganese pyrophosphate according to claim 1 or 2, it is characterized in that: in step (5), described non-oxidizing atmosphere is one or more in argon gas, nitrogen, helium, hydrogen or carbon monoxide.
7. core shell structure lithium ion battery negative material manganese pyrophosphate according to claim 1 or 2, it is characterized in that: in step (1), described Organic Mn source is disodium ethylene diamine tetraacetate manganese and/or manganese acetylacetonate.
8. core shell structure lithium ion battery negative material manganese pyrophosphate according to claim 3, it is characterized in that: in step (1), described Organic Mn source is disodium ethylene diamine tetraacetate manganese and/or manganese acetylacetonate.
9. core shell structure lithium ion battery negative material manganese pyrophosphate according to claim 4, it is characterized in that: in step (1), described Organic Mn source is disodium ethylene diamine tetraacetate manganese and/or manganese acetylacetonate.
10. according to one of claim 1 ~ 9 described core shell structure lithium ion battery negative material manganese pyrophosphate, it is characterized in that: in step (1), described phosphorus source is one or more in ammonium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium phosphate, phosphoric acid or pyrophosphoric acid.
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| CN110589789A (en) * | 2019-09-07 | 2019-12-20 | 中南大学 | Preparation method of negative electrode material nano needle-shaped antimony phosphate |
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107697895A (en) * | 2017-09-13 | 2018-02-16 | 苏州安锰新能源科技有限公司 | A kind of nanoporous manganese pyrophosphate and preparation method thereof |
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| 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 |
| CN110098383A (en) * | 2018-01-29 | 2019-08-06 | 宁德新能源科技有限公司 | Positive electrode and preparation method thereof, anode and lithium ion battery |
| CN109853085A (en) * | 2018-12-13 | 2019-06-07 | 大连理工大学 | A kind of regulation method of amorphous carbon-reproducibility graphene oxide-cobaltosic oxide package structure composite nano fiber conductance |
| 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 |
| CN110589789A (en) * | 2019-09-07 | 2019-12-20 | 中南大学 | Preparation method of negative electrode material nano needle-shaped antimony phosphate |
| CN110589789B (en) * | 2019-09-07 | 2023-02-17 | 中南大学 | Preparation method of negative electrode material nano needle-shaped antimony phosphate |
| CN111900382A (en) * | 2020-07-21 | 2020-11-06 | 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 |
| CN113877611A (en) * | 2021-09-26 | 2022-01-04 | 安徽工业大学 | Phosphoric acid modified manganese oxide supported catalyst and preparation method 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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