CN104103832A - Preparation method for LiFePO4-LiVPO4F for cathode material for lithium ion battery - Google Patents
Preparation method for LiFePO4-LiVPO4F for cathode material for lithium ion battery Download PDFInfo
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Abstract
A preparation method for LiFePO4-LiVPO4F for the cathode material for a lithium ion battery comprises the following steps: (1) an iron source solution containing iron and a vanadium source solution containing vanadium are simultaneously added into a reactor for reaction so as to generate amorphous ferric vanadate precipitate, wherein the molar ratio of iron to vanadium is 1:1; (2) amorphous ferric vanadate precipitate is sintered for 4-10 in air at the temperature of 400-650 DEG C; (3) the obtained amorphous ferric vanadate precursor is mixed with a lithium source, a fluorine source, a phosphorus source and a carbon source uniformly; (4) the mixture is placed in a tubular sintering furnace for sintering for 4-20 in non-oxidizing atmosphere at the temperature of 600-800 DEG C, and then cooled to the room temperature. According to the cathode composite material obtained through the preparation method provided by the invention, the high specific capacity of LiFePO4 and the rapid lithium-ion channel of LiVPO4F are combined with the relatively high electronic conductivity and good cycling stability to form the novel cathode composite material, which is excellent in electrochemical performance.
Description
Technical field
The present invention relates to a kind of preparation method of anode material for lithium-ion batteries, especially relate to a kind of preparation method of lithium ferrous phosphate as anode material of lithium ion battery-fluorophosphoric acid vanadium lithium.
Background technology
LiFePO 4 (LiFePO
4), fluorophosphoric acid vanadium lithium (LiVPO
4f) be all Olivine-type Cathode Material in Li-ion Batteries, belong to phosphate-based positive electrode.LiFePO
4there is higher specific discharge capacity (176mAh/g) and discharge platform (3.4V stably
vsli
+), and raw material is cheap and easy to get, at present commercial applications.But the electronic conductivity that it is lower and ionic conductivity limit its specific discharge capacity and cyclical stability when large multiplying power discharging greatly.Fluorophosphoric acid vanadium lithium passes through VO
4f
2octahedron and PO
4tetrahedron forms space three-dimensional network configuration, has two crystallization position lithium ions to embed, and therefore has excellent charge-discharge performance and high rate capability.Fluorine has very strong electronegativity, it and vanadium ion are connected to form strong V-F key, be connected to form Li-F key with lithium, in the de-embedding process of lithium ion, provide stable reversible construction, can reduce the surface erosion of electrolyte to electrode material adding of fluorine simultaneously, make material there is good cyclical stability, the theoretical specific capacity lower (156mAh/g) yet it discharges, actual specific capacity is lower, and the technique of its conventional two steps synthetic (CN 103840157 A) is loaded down with trivial details, also easily introduces the impurity such as phosphoric acid vanadium lithium.
Summary of the invention
Technical problem to be solved by this invention is, overcomes the deficiencies in the prior art, provides that a kind of chemical property is excellent, the preparation method of the better simply lithium ferrous phosphate as anode material of lithium ion battery-fluorophosphoric acid vanadium lithium of synthetic method.
The technical solution adopted for the present invention to solve the technical problems is: the preparation method of lithium ferrous phosphate as anode material of lithium ion battery-fluorophosphoric acid vanadium lithium, comprises the following steps:
(1) by containing the source of iron solution of ferro element with containing the vanadium source solution of v element, by the mol ratio of ferro element and v element, be 1:1, join in reactor simultaneously, and to control reactor mixing speed be 100-400rpm, with ammoniacal liquor regulator solution pH, be 4-7, reaction 2-4 hour, generates amorphous state ferric vandate precipitation, Separation of Solid and Liquid;
(2) step (1) gained amorphous state ferric vandate is deposited in to 400-650 ℃ of (preferably 500-600 ℃) sintering 6-8h in air, obtains crystalline state ferric vandate presoma;
(3) step (2) gained crystalline state ferric vandate presoma is mixed according to mol ratio 1:2:1:2:1-5 of ferro element, elemental lithium, fluorine element, P elements and carbon in ferric vandate with lithium source, fluorine source, phosphorus source and carbon source;
(4) mixture of processing through step (3) is placed in pipe type sintering furnace through grinding, compressing tablet, in lower 600 ℃-800 ℃ of nonoxidizing atmosphere (preferably 650 ℃-750 ℃) the preferred 6-15h of sintering 4-20h(), cool to room temperature, obtains LiFePO 4-fluorophosphoric acid vanadium lithium composite positive pole.
Further, in step (1), described source of iron is a kind of in ferric sulfate, ferrous sulfate, ferric nitrate, iron chloride, ferrous oxalate.
Further, in step (1), described vanadium source is a kind of in ammonium metavanadate, ammonium vanadate, sodium vanadate, potassium vanadate, vanadic sulfate, oxalic acid vanadyl.
Further, in step (3), described lithium source is a kind of in lithium hydroxide, lithium carbonate, lithium fluoride, lithium dihydrogen phosphate, lithium acetate.
Further, in step (3), described fluorine source is a kind of in ammonium fluoride, lithium fluoride, sodium fluoride.
Further, in step (3), described phosphorus source is a kind of in ammonium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium phosphate, phosphoric acid, pyrophosphoric acid.
Further, in step (3), described carbon source is a kind of in oxalic acid, glucose, citric acid, ascorbic acid, sucrose.
Further, in step (4), a kind of for in argon gas, nitrogen, helium of described nonoxidizing atmosphere.
The present invention is by LiFePO 4, two kinds of fluorophosphoric acid vanadium lithiums have different advantages, the material of performance difference carries out compound, make full use of the height ratio capacity of LiFePO 4 and the quick lithium ion passage of fluorophosphoric acid vanadium lithium, relatively high electronic conductivity and good cyclical stability, formation has the composite material of mutual supplement with each other's advantages, and composite material can produce by the synergy between each constituent element multiple complex effect, by the varistructure parameter of regulation and control composite material, utilize its complex effect can make material at physical function, the aspects such as chemistry and mechanical property obtain best overall performance.
The present invention utilizes coprecipitation to prepare the ferric vandate with nano-scale, then utilizes ferric vandate and lithium source, fluorine source, carbon source to synthesize LiFePO 4-fluorophosphoric acid vanadium lithium anode composite material.This anode composite material, the quick lithium ion passage of the height ratio capacity of LiFePO 4 and fluorophosphoric acid vanadium lithium and relatively high electronic conductivity and good cyclical stability are combined and form novel anode composite material, and this composite positive pole chemical property is excellent.
Accompanying drawing explanation
Fig. 1 is 0.1C, 1C, the 5C first charge-discharge curve of gained positive electrode assembled battery in the embodiment of the present invention 1;
Fig. 2 is the cycle graph of the electrochemistry high rate performance of gained positive electrode assembled battery in the embodiment of the present invention 1;
Fig. 3 is the cyclic voltammogram of gained positive electrode assembled battery in the embodiment of the present invention 1.
Embodiment
Below in conjunction with embodiment, the invention will be further described.
Embodiment 1
The present embodiment comprises the following steps:
(1) by 0.01mol ferric sulfate, 0.01mol ammonium metavanadate, be dissolved in respectively in the deionized water of 1000mL, then join in reactor simultaneously, and to control reactor mixing speed be 400rpm, with ammoniacal liquor regulator solution pH, be 6, reaction 6h, generate amorphous state ferric vandate precipitation, Separation of Solid and Liquid;
(2) step (1) gained amorphous state ferric vandate is deposited in to 550 ℃ of sintering 6h in air, obtains crystalline state ferric vandate presoma;
(3) by step (2) gained crystalline state ferric vandate presoma and lithium hydroxide, lithium fluoride, ammonium dihydrogen phosphate, citric acid is that 1:2:1:2:4 mixes according to the mol ratio of ferro element, elemental lithium, fluorine element, P elements and carbon in ferric vandate;
(4) mixture of processing through step (3) is fully ground to uniform powder in agate mortar, compressing tablet is placed in pipe type sintering furnace, under argon gas atmosphere, in 750 ℃ of sintering 10h, be then naturally cooled to room temperature, obtain LiFePO 4-fluorophosphoric acid vanadium lithium composite positive pole.
The assembling of battery: the LiFePO 4-fluorophosphoric acid vanadium lithium composite positive pole that takes 0.24g gained, add 0.03gSuper-P to make conductive agent and 0.03gPVDF(HSV-900) make binding agent, after fully grinding, add NMP2mL to disperse to mix, size mixing to after evenly on the thick aluminium foil of 16 μ m slurry be made into positive plate, in anaerobism glove box, take metal lithium sheet as negative pole, take Celgard 2300 as barrier film, 1mol/L LiPF
6/ EC: DMC: EMC(volume ratio 1: 1: 1) be electrolyte, be assembled into the button cell of CR2025, battery is surveyed to its charge/discharge capacity and high rate performance in 3.0V～4.5V voltage range, wherein 0.1C first discharge specific capacity is 160mAh/g, 1C first discharge specific capacity is 148.7mAh/g, 5C first discharge specific capacity is 112.4mAh/g, and specific discharge capacity is 125 mAh/g after 100 times.Fig. 1 is 0.1C, 1C, the 5C first charge-discharge curve of gained positive electrode assembled battery in the embodiment of the present invention 1; Fig. 2 is the cycle graph of the electrochemistry high rate performance of gained positive electrode assembled battery in the embodiment of the present invention 1; Fig. 3 is the cyclic voltammogram of gained positive electrode assembled battery in the embodiment of the present invention 1.
A kind of preparation method of nano-sheet lithium ion battery anode material vanadium lithium phosphate is disclosed with contrasting of prior art: CN 103840157 A, in embodiment 1, gained fluorophosphoric acid vanadium lithium anode material is assembled into battery, 0.1C first discharge specific capacity is only 143.3mAh/g, and 1C first discharge specific capacity is only 119.4mAh/g.The chemical property that visible gained positive electrode of the present invention is assembled into battery is better than prior art.
Embodiment 2
The present embodiment comprises the following steps:
(1) by 0.01mol ferric nitrate, 0.01mol ammonium metavanadate, be dissolved in respectively in the deionized water of 1000mL, then join in reactor simultaneously, and to control reactor mixing speed be 300rpm, with ammoniacal liquor, regulating pH is 4, reaction 6h, generate amorphous state ferric vandate precipitation, Separation of Solid and Liquid;
(2) step (1) gained amorphous state ferric vandate is deposited in to 650 ℃ of sintering 4h in air and obtains crystalline state ferric vandate presoma;
(3) by step (2) gained crystalline state ferric vandate presoma, according to the mol ratio of ferro element, elemental lithium, fluorine element, P elements and carbon in ferric vandate, be that 1:2:1:2:5 mixes with lithium carbonate, ammonium fluoride, ammonium dihydrogen phosphate, oxalic acid;
(4) mixture of processing through step (3) is fully ground to uniform powder in agate mortar, compressing tablet is placed in pipe type sintering furnace, under argon gas atmosphere, in 800 ℃ of sintering 4h, be then naturally cooled to room temperature, obtain LiFePO 4-fluorophosphoric acid vanadium lithium composite positive pole.
The assembling of battery: the LiFePO 4-fluorophosphoric acid vanadium lithium anode composite material that takes 0.24g gained, add 0.03gSuper-P to make conductive agent and 0.03gPVDF(HSV-900) make binding agent, after fully grinding, add NMP2mL to disperse to mix, size mixing to after evenly on the thick aluminium foil of 16 μ m slurry be made into positive plate, in anaerobism glove box, take metal lithium sheet as negative pole, take Celgard 2300 as barrier film, 1mol/L LiPF
6/ EC: DMC: EMC(volume ratio 1: 1: 1) be electrolyte, be assembled into the button cell of CR2025, battery is surveyed to its charge/discharge capacity and high rate performance in 3.0V～4.5V voltage range, wherein 0.1C first discharge specific capacity is 160.3mAh/g, 1C first discharge specific capacity is 139.4mAh/g, 5C first discharge specific capacity is 109.4mAh/g, and after 100 circulations, specific discharge capacity is 102 mAh/g.
Embodiment 3
The present embodiment comprises the following steps:
(1) by 0.01mol iron chloride, 0.01mol sodium vanadate, be dissolved in respectively in the deionized water of 1000mL, then join in reactor simultaneously, and to control reactor mixing speed be 100rpm, with ammoniacal liquor, regulating pH is 7, reaction 1h, generate amorphous state ferric vandate precipitation, Separation of Solid and Liquid;
(2) step (1) gained amorphous state ferric vandate is deposited in to 400 ℃ of sintering 10h in air, obtains crystalline state ferric vandate presoma;
(3) by step (2) gained crystalline state ferric vandate presoma, according to the mol ratio of ferro element, elemental lithium, fluorine element, P elements and carbon in ferric vandate, be that 1:2:1:2:1 mixes with lithium hydroxide, ammonium fluoride, ammonium dihydrogen phosphate, oxalic acid;
(4) mixture of processing through step (3) is fully ground to uniform powder in agate mortar, compressing tablet is placed in pipe type sintering furnace, under argon gas atmosphere, in 600 ℃ of sintering 20h, be then naturally cooled to room temperature, obtain LiFePO 4-fluorophosphoric acid vanadium lithium anode composite material.
The assembling of battery: the LiFePO 4-fluorophosphoric acid vanadium lithium anode composite material that takes 0.24g gained, add 0.03gSuper-P to make conductive agent and 0.03gPVDF(HSV-900) make binding agent, after fully grinding, add NMP2mL to disperse to mix, size mixing to after evenly on the thick aluminium foil of 16 μ m slurry be made into positive plate, in anaerobism glove box, take metal lithium sheet as negative pole, take Celgard 2300 as barrier film, 1mol/L LiPF
6/ EC: DMC: EMC(volume ratio 1: 1: 1) be electrolyte, be assembled into the button cell of CR2025, battery is surveyed to its charge/discharge capacity and high rate performance in 3.0V～4.5V voltage range, wherein 0.1C first discharge specific capacity is 163.6mAh/g, 1C first discharge specific capacity is 149.4mAh/g, 5C first discharge specific capacity is 119.7mAh/g, and after 100 circulations, specific discharge capacity is 122 mAh/g.
Embodiment 4
The present embodiment comprises the following steps:
(1) by 0.01mol ferric sulfate, 0.02mol sodium vanadate, be dissolved in respectively in the deionized water of 1000mL, then join in reactor simultaneously, and to control reactor mixing speed be 300rpm, with ammoniacal liquor, regulating pH is 6, reaction 5h, generate amorphous state ferric vandate precipitation, Separation of Solid and Liquid;
(2) step (1) gained amorphous state ferric vandate is deposited in to 500 ℃ of sintering 8h in air, obtains crystalline state ferric vandate presoma;
(3) step (2) gained crystalline state ferric vandate presoma is mixed according to the mol ratio 1:2:1:2:2 of ferro element, elemental lithium, fluorine element, P elements and carbon in ferric vandate with lithium hydroxide, ammonium fluoride, ammonium dihydrogen phosphate, oxalic acid;
(4) mixture of processing through step (3) is fully ground to uniform powder in agate mortar, compressing tablet is placed in pipe type sintering furnace, under argon gas atmosphere, in 700 ℃ of sintering 15h, be then naturally cooled to room temperature, obtain LiFePO 4-fluorophosphoric acid vanadium lithium anode composite material.
The assembling of battery: the LiFePO 4-fluorophosphoric acid vanadium lithium anode composite material that takes 0.24g gained, add 0.03gSuper-P to make conductive agent and 0.03gPVDF(HSV-900) make binding agent, after fully grinding, add NMP2mL to disperse to mix, size mixing to after evenly on the thick aluminium foil of 16 μ m slurry be made into positive plate, in anaerobism glove box, take metal lithium sheet as negative pole, take Celgard 2300 as barrier film, 1mol/L LiPF
6/ EC: DMC: EMC(volume ratio 1: 1: 1) be electrolyte, be assembled into the button cell of CR2025, battery is surveyed to its charge/discharge capacity and high rate performance in 3.0V～4.5V voltage range, wherein 0.1C first discharge specific capacity is 170.3mAh/g, 1C first discharge specific capacity is 159.4mAh/g, 5C first discharge specific capacity is 142.4mAh/g, and after 100 circulations, specific discharge capacity is 138.5mAh/g.
Embodiment 5
The present embodiment comprises the following steps:
(1) by 0.01mol ferric nitrate, 0.01mol sodium vanadate, be dissolved in respectively in the deionized water of 1000mL, then join in reactor simultaneously, and to control reactor mixing speed be 200rpm, with ammoniacal liquor, regulating pH is 5, reaction 3h, generate amorphous state ferric vandate precipitation, Separation of Solid and Liquid;
(2) step (1) gained amorphous state ferric vandate is deposited in to 600 ℃ of sintering 5h in air, obtains crystalline state ferric vandate presoma;
(3) by step (2) gained crystalline state ferric vandate presoma, according to the mol ratio of ferro element, elemental lithium, fluorine element, P elements and carbon in ferric vandate, be that 1:2:1:2:4 mixes with lithium hydroxide, sodium fluoride, diammonium hydrogen phosphate, ascorbic acid;
(4) mixture of step (3) being processed is fully ground to uniform powder in agate mortar, compressing tablet is placed in pipe type sintering furnace, under argon gas atmosphere, in 750 ℃ of sintering 6h, be then naturally cooled to room temperature, obtain LiFePO 4-fluorophosphoric acid vanadium lithium anode composite material.
The assembling of battery: the LiFePO 4-fluorophosphoric acid vanadium lithium anode composite material that takes 0.24g gained, add 0.03gSuper-P to make conductive agent and 0.03gPVDF(HSV-900) make binding agent, after fully grinding, add NMP2mL to disperse to mix, size mixing to after evenly on the thick aluminium foil of 16 μ m slurry be made into positive plate, in anaerobism glove box, take metal lithium sheet as negative pole, take Celgard 2300 as barrier film, 1mol/L LiPF
6/ EC: DMC: EMC(volume ratio 1: 1: 1) be electrolyte, be assembled into the button cell of CR2025, battery is surveyed to its charge/discharge capacity and high rate performance in 3.0V～4.5V voltage range, wherein 0.1C first discharge specific capacity is 168.3mAh/g, 1C first discharge specific capacity is 149.4mAh/g, 5C first discharge specific capacity is 128.7mAh/g, and after 100 circulations, specific discharge capacity is 132 mAh/g.
Claims (10)
1. the preparation method of lithium ferrous phosphate as anode material of lithium ion battery-fluorophosphoric acid vanadium lithium, is characterized in that, comprises the following steps:
(1) by containing the source of iron solution of ferro element with containing the vanadium source solution of v element, by the mol ratio of ferro element and v element, be 1:1, join in reactor simultaneously, and to control reactor mixing speed be 100-400rpm, with ammoniacal liquor regulator solution pH, be 4-7, reaction 1-6h, generates amorphous state ferric vandate precipitation, Separation of Solid and Liquid;
(2) step (1) gained amorphous state ferric vandate is deposited in to 400-650 ℃ of sintering 4-10h in air, obtains crystalline state ferric vandate presoma;
(3) step (2) gained crystalline state ferric vandate presoma is mixed according to mol ratio 1:2:1:2:1-5 of ferro element, elemental lithium, fluorine element, P elements and carbon in ferric vandate with lithium source, fluorine source, phosphorus source and carbon source;
(4) mixture of processing through step (3) is placed in pipe type sintering furnace through grinding, compressing tablet, in lower 600 ℃ of-800 ℃ of sintering 4-20h of nonoxidizing atmosphere, cool to room temperature, obtains LiFePO 4-fluorophosphoric acid vanadium lithium composite positive pole.
2. the preparation method of lithium ferrous phosphate as anode material of lithium ion battery-fluorophosphoric acid vanadium lithium according to claim 1, is characterized in that, in step (1), described source of iron is a kind of in ferric sulfate, ferrous sulfate, ferric nitrate, iron chloride, ferrous oxalate.
3. the preparation method of lithium ferrous phosphate as anode material of lithium ion battery-fluorophosphoric acid vanadium lithium according to claim 1 and 2, it is characterized in that, in step (1), described vanadium source is a kind of in ammonium metavanadate, ammonium vanadate, sodium vanadate, potassium vanadate, vanadic sulfate, oxalic acid vanadyl.
4. the preparation method of lithium ferrous phosphate as anode material of lithium ion battery-fluorophosphoric acid vanadium lithium according to claim 1 and 2, it is characterized in that, in step (3), described lithium source is a kind of in lithium hydroxide, lithium carbonate, lithium fluoride, lithium dihydrogen phosphate, lithium acetate.
5. the preparation method of lithium ferrous phosphate as anode material of lithium ion battery-fluorophosphoric acid vanadium lithium according to claim 1 and 2, is characterized in that, in step (3), described fluorine source is a kind of in ammonium fluoride, lithium fluoride, sodium fluoride.
6. the preparation method of lithium ferrous phosphate as anode material of lithium ion battery-fluorophosphoric acid vanadium lithium according to claim 1 and 2, it is characterized in that, in step (3), described phosphorus source is a kind of in ammonium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium phosphate, phosphoric acid, pyrophosphoric acid.
7. the preparation method of lithium ferrous phosphate as anode material of lithium ion battery-fluorophosphoric acid vanadium lithium according to claim 1 and 2, is characterized in that, in step (3), described carbon source is a kind of in oxalic acid, glucose, citric acid, ascorbic acid, sucrose.
8. the preparation method of lithium ferrous phosphate as anode material of lithium ion battery-fluorophosphoric acid vanadium lithium according to claim 1 and 2, is characterized in that, in step (4), and a kind of for in argon gas, nitrogen, helium of described nonoxidizing atmosphere.
9. the preparation method of lithium ferrous phosphate as anode material of lithium ion battery-fluorophosphoric acid vanadium lithium according to claim 1 and 2, is characterized in that, in step (2), gained amorphous state ferric vandate is deposited in to 500-600 ℃ of sintering 6-8h in air.
10. the preparation method of lithium ferrous phosphate as anode material of lithium ion battery-fluorophosphoric acid vanadium lithium according to claim 1 and 2, is characterized in that, in step (4), in lower 650 ℃ of-750 ℃ of sintering 6-15h of nonoxidizing atmosphere.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| RU2619600C2 (en) * | 2015-09-28 | 2017-05-17 | Федеральное государственное бюджетное образовательное учреждение высшего образования "Московский государственный университет имени М.В. Ломоносова" (МГУ) | Electrode material for metal-ion battery, method of its production, electrode and electrode material based battery |
| CN106920947A (en) * | 2017-04-20 | 2017-07-04 | 哈尔滨工业大学 | A kind of fluorophosphate Li-like ions electron mixed conductor modified cobalt acid lithium composite material and preparation method thereof |
| CN107994211A (en) * | 2017-10-19 | 2018-05-04 | 北大先行科技产业有限公司 | A kind of preparation method of anode material for lithium-ion batteries |
| CN108682811A (en) * | 2018-05-10 | 2018-10-19 | 中南大学 | A kind of lithium manganese phosphate/fluorophosphoric acid vanadium lithium/carbon composite anode material and preparation method thereof |
| CN109286005A (en) * | 2018-09-14 | 2019-01-29 | 中南大学 | A kind of LiFePO4/fluorophosphoric acid vanadium lithium/carbon composite anode material and preparation method thereof |
| CN112736226A (en) * | 2020-12-28 | 2021-04-30 | 大连博融新材料有限公司 | Vanadium-doped carbon-coated lithium iron phosphate, and preparation method and application thereof |
| WO2022093486A1 (en) * | 2020-10-29 | 2022-05-05 | Saft America | Blended cathode materials for secondary batteries |
| CN115092902A (en) * | 2022-07-04 | 2022-09-23 | 中南大学 | Method for preparing lithium manganese iron phosphate cathode material by utilizing iron-rich manganese slag |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1803593A (en) * | 2005-12-19 | 2006-07-19 | 南开大学 | Method for preparing anode material vanadium lithium fluorinated phosphate of lithium ion secondary battery |
| CN101114709A (en) * | 2007-08-10 | 2008-01-30 | 武汉大学 | Lithium ion battery composite anode material LiFePO4-Li3V2(PO4)3/C and method for making same |
| CN101262058A (en) * | 2008-04-15 | 2008-09-10 | 中南大学 | An anode material for compound lithium ion battery |
| DE102012022606A1 (en) * | 2012-11-19 | 2014-05-22 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Coated particulate electrode material, useful in lithium rechargeable batteries and/or double-layer capacitors, comprises particulate electrode material comprising lithium-intercalating and lithium deintercalating substances |
-
2014
- 2014-07-23 CN CN201410351883.0A patent/CN104103832A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1803593A (en) * | 2005-12-19 | 2006-07-19 | 南开大学 | Method for preparing anode material vanadium lithium fluorinated phosphate of lithium ion secondary battery |
| CN101114709A (en) * | 2007-08-10 | 2008-01-30 | 武汉大学 | Lithium ion battery composite anode material LiFePO4-Li3V2(PO4)3/C and method for making same |
| CN101262058A (en) * | 2008-04-15 | 2008-09-10 | 中南大学 | An anode material for compound lithium ion battery |
| DE102012022606A1 (en) * | 2012-11-19 | 2014-05-22 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Coated particulate electrode material, useful in lithium rechargeable batteries and/or double-layer capacitors, comprises particulate electrode material comprising lithium-intercalating and lithium deintercalating substances |
Non-Patent Citations (1)
| Title |
|---|
| 郑俊超: "锂离子电池正极材料LiFePO4、Li3V2(PO4)3及xLiFePO4•yLi3V2(PO4)3的制备与性能研究", 《中国博士学位论文全文数据库（电子期刊）工程科技Ⅱ辑》, 15 November 2010 (2010-11-15) * |
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| RU2619600C2 (en) * | 2015-09-28 | 2017-05-17 | Федеральное государственное бюджетное образовательное учреждение высшего образования "Московский государственный университет имени М.В. Ломоносова" (МГУ) | Electrode material for metal-ion battery, method of its production, electrode and electrode material based battery |
| CN106920947A (en) * | 2017-04-20 | 2017-07-04 | 哈尔滨工业大学 | A kind of fluorophosphate Li-like ions electron mixed conductor modified cobalt acid lithium composite material and preparation method thereof |
| CN106920947B (en) * | 2017-04-20 | 2019-07-16 | 哈尔滨工业大学 | A kind of fluorophosphate Li-like ions-electron mixed conductor modified cobalt acid lithium composite material and preparation method thereof |
| CN107994211A (en) * | 2017-10-19 | 2018-05-04 | 北大先行科技产业有限公司 | A kind of preparation method of anode material for lithium-ion batteries |
| CN108682811A (en) * | 2018-05-10 | 2018-10-19 | 中南大学 | A kind of lithium manganese phosphate/fluorophosphoric acid vanadium lithium/carbon composite anode material and preparation method thereof |
| CN109286005A (en) * | 2018-09-14 | 2019-01-29 | 中南大学 | A kind of LiFePO4/fluorophosphoric acid vanadium lithium/carbon composite anode material and preparation method thereof |
| CN109286005B (en) * | 2018-09-14 | 2021-07-16 | 中南大学 | Lithium iron phosphate/lithium vanadium fluorophosphate/carbon composite cathode material and preparation method thereof |
| WO2022093486A1 (en) * | 2020-10-29 | 2022-05-05 | Saft America | Blended cathode materials for secondary batteries |
| CN112736226A (en) * | 2020-12-28 | 2021-04-30 | 大连博融新材料有限公司 | Vanadium-doped carbon-coated lithium iron phosphate, and preparation method and application thereof |
| CN115092902A (en) * | 2022-07-04 | 2022-09-23 | 中南大学 | Method for preparing lithium manganese iron phosphate cathode material by utilizing iron-rich manganese slag |
| CN115092902B (en) * | 2022-07-04 | 2024-04-12 | 中南大学 | Method for preparing lithium iron manganese phosphate positive electrode material by using iron-manganese-rich slag |
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