CN115432685A - Ferro-phosphorus lithium ion battery cathode material and preparation method and application thereof - Google Patents
Ferro-phosphorus lithium ion battery cathode material and preparation method and application thereof Download PDFInfo
- Publication number
- CN115432685A CN115432685A CN202211107860.6A CN202211107860A CN115432685A CN 115432685 A CN115432685 A CN 115432685A CN 202211107860 A CN202211107860 A CN 202211107860A CN 115432685 A CN115432685 A CN 115432685A
- Authority
- CN
- China
- Prior art keywords
- preparation
- lithium ion
- ion battery
- solution
- ferrophosphorus
- 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
Links
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 43
- 239000010406 cathode material Substances 0.000 title claims description 29
- 229910052698 phosphorus Inorganic materials 0.000 title description 9
- 239000011574 phosphorus Substances 0.000 title description 9
- 239000000243 solution Substances 0.000 claims abstract description 85
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 71
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910052742 iron Inorganic materials 0.000 claims abstract description 32
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 31
- 239000010405 anode material Substances 0.000 claims abstract description 29
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 25
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000002156 mixing Methods 0.000 claims abstract description 24
- 239000000463 material Substances 0.000 claims abstract description 17
- 239000012266 salt solution Substances 0.000 claims abstract description 17
- 238000001354 calcination Methods 0.000 claims abstract description 16
- 239000011259 mixed solution Substances 0.000 claims abstract description 14
- 239000000203 mixture Substances 0.000 claims abstract description 13
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 claims abstract description 12
- 235000011180 diphosphates Nutrition 0.000 claims abstract description 12
- 239000002253 acid Substances 0.000 claims abstract description 11
- 150000002696 manganese Chemical class 0.000 claims abstract description 11
- 239000011261 inert gas Substances 0.000 claims abstract description 10
- 230000002378 acidificating effect Effects 0.000 claims abstract description 6
- 150000002505 iron Chemical class 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 23
- 229910017604 nitric acid Inorganic materials 0.000 claims description 23
- 238000003756 stirring Methods 0.000 claims description 21
- VKFFEYLSKIYTSJ-UHFFFAOYSA-N tetraazanium;phosphonato phosphate Chemical compound [NH4+].[NH4+].[NH4+].[NH4+].[O-]P([O-])(=O)OP([O-])([O-])=O VKFFEYLSKIYTSJ-UHFFFAOYSA-N 0.000 claims description 11
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 10
- MQMHJMFHCMWGNS-UHFFFAOYSA-N phosphanylidynemanganese Chemical compound [Mn]#P MQMHJMFHCMWGNS-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 5
- 238000001694 spray drying Methods 0.000 claims description 4
- 238000010979 pH adjustment Methods 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 abstract 1
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 32
- 238000006243 chemical reaction Methods 0.000 description 29
- 239000011572 manganese Substances 0.000 description 21
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 11
- 238000001027 hydrothermal synthesis Methods 0.000 description 11
- 229910052748 manganese Inorganic materials 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 8
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 description 7
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 7
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 6
- 239000008103 glucose Substances 0.000 description 6
- -1 manganese pyrophosphate ions Chemical class 0.000 description 6
- 229930006000 Sucrose Natural products 0.000 description 5
- 239000005720 sucrose Substances 0.000 description 5
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 125000000185 sucrose group Chemical group 0.000 description 2
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 229910001447 ferric ion Inorganic materials 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- 229940071125 manganese acetate Drugs 0.000 description 1
- 229910001437 manganese ion Inorganic materials 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/45—Phosphates containing plural metal, or metal and ammonium
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- 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)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a ferrophosphorus lithium ion battery anode material and a preparation method and application thereof, wherein the preparation method comprises the following steps: (1) Mixing a water-soluble manganese salt solution and a water-soluble pyrophosphate solution, adding an acid solution to adjust the pH value to be acidic, and then adding a water-soluble iron salt solution to react to obtain a mixed solution; (2) Mixing the mixed solution obtained in the step (1) with an iron source, a lithium source and a carbon source to obtain a mixture, and drying to obtain a dried material; (3) And (3) calcining the dried material obtained in the step (2) in inert gas to obtain the catalyst. The ferrophosphorus lithium ion prepared by the preparation method has higher specific capacity and cycle performance.
Description
Technical Field
The invention belongs to the technical field of lithium battery anode materials, and particularly relates to a ferrophosphorus lithium ion battery anode material and a preparation method and application thereof.
Background
The anode materials adopted by the existing lithium ion battery mainly comprise lithium iron phosphate, lithium manganate, lithium cobaltate, ternary anode materials and the like. The lithium iron phosphate material has attracted much attention as a lithium ion battery anode material due to its high structural stability, and is a cathode material found at present to have good safety. However, the discharge capacity of the existing ferrophosphorus lithium ion battery anode material is still low, and the existing ferrophosphorus lithium ion battery anode material is difficult to counterbalance with a ternary anode material. Therefore, how to prepare a high-capacity ferrophosphorus lithium ion battery cathode material with reliable quality is a problem to be solved urgently at present.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art. Therefore, the invention provides a ferrophosphorus lithium ion battery anode material, a preparation method and application thereof, and ferrophosphorus lithium ions prepared by the preparation method have higher specific capacity and cycle performance.
The technical purpose of the invention is realized by the following technical scheme:
a preparation method of a ferrophosphorus lithium ion battery anode material comprises the following steps:
(1) Mixing a water-soluble manganese salt solution and a water-soluble pyrophosphate solution, adding an acid solution to adjust the pH value to be acidic, and then adding a water-soluble iron salt solution to react to obtain a mixed solution; (2) Mixing the mixed solution obtained in the step (1) with an iron source, a lithium source and a carbon source to obtain a mixture, and drying to obtain a dried material; (3) And (3) calcining the dried material obtained in the step (2) in inert gas to obtain the ferrophosphorus lithium ion battery anode material.
Preferably, in the step (1), the water-soluble manganese salt solution is a manganese nitrate solution, the water-soluble pyrophosphate solution is a tetra-ammonium pyrophosphate solution, and the acid solution is a nitric acid solution.
Preferably, in the step (1), the concentration of the water-soluble manganese salt solution is 0.5-3.0mol/L.
Further preferably, in the step (1), the concentration of the water-soluble manganese salt solution is 1 to 2.0mol/L.
Preferably, in the step (1), the concentration of the water-soluble pyrophosphate solution is 0.5-3.0mol/L.
Further preferably, in the step (1), the concentration of the water-soluble pyrophosphate solution is 1 to 2.0mol/L.
Preferably, in the step (1), the concentration of the acid solution is 0.1-1.0mol/L.
Further preferably, in the step (1), the concentration of the acid solution is 0.1-0.5mol/L.
Preferably, in the step (1), the acid solution is a nitric acid solution.
Preferably, in the step (1), the water-soluble manganese salt solution and the water-soluble pyrophosphate solution are mixed according to the manganese-phosphorus molar ratio of 1 (2-5).
Further preferably, in the step (1), the water-soluble manganese salt solution and the water-soluble pyrophosphate solution are mixed according to a manganese-phosphorus molar ratio of 1.
Preferably, in the step (1), the acid is added dropwise under stirring, the adding speed is 10-50mL/h, and the stirring speed is 10-50r/min.
Further preferably, in the step (1), the acid is added dropwise under stirring, the adding rate is 20-40mL/h, and the stirring speed is 25-50r/min.
Preferably, in the step (1), the pH adjustment to be acidic means that the pH is adjusted to 1.0 to 3.0.
Further preferably, in the step (1), the pH adjustment to be acidic means that the pH is adjusted to 1.5 to 1.7.
Preferably, in the step (1), the water-soluble iron salt solution is added dropwise under stirring, the adding speed is 30-100mL/h, and the stirring speed is 20-100r/min.
Further preferably, in the step (1), the water-soluble iron salt solution is added dropwise under stirring, the adding rate is 40-80mL/h, and the stirring speed is 30-60r/min.
Preferably, in step (1), the temperature of the reaction is 80 to 150 ℃.
Further preferably, in the step (1), the temperature of the reaction is 100 to 120 ℃.
Preferably, in the step (1), the reaction is carried out in a reaction kettle, and the pressure in the reaction kettle is controlled to be not higher than 0.3MPa.
Preferably, in the step (1), when the molar ratio of iron to manganese in the mixed solution is 1.
Preferably, in the step (2), fe, mn, li and the carbon source =2 in the mixture (1.0-6.5) and (1.0-2.0).
Further preferably, in the step (2), the ratio of Fe, mn and Li to the carbon source = 2.
Preferably, in the step (2), the drying manner is spray drying.
Preferably, in the step (2), the iron source is at least one of iron nitrate and iron acetate.
Preferably, in the step (2), the lithium source is at least one of lithium acetate and lithium nitrate.
Preferably, in the step (2), the carbon source is at least one of glucose and sucrose.
Preferably, in the step (3), the calcining temperature is 500-1000 ℃, and the calcining time is 10-30h.
Further preferably, in the step (3), the calcining temperature is 600-850 ℃ and the calcining time is 12-24h.
Preferably, the preparation method of the ferrophosphorus lithium ion battery cathode material comprises the following steps:
(1) Preparing a nitric acid solution with the concentration of 0.1-0.5 mol/L;
(2) Preparing a tetraammonium pyrophosphate solution with the concentration of 1-2.0 mol/L;
(3) Preparing a manganese nitrate solution with the concentration of 1-2.0 mol/L;
(4) Mixing the solutions prepared in the steps (2) and (3) according to the molar ratio of manganese to phosphorus of 1;
(5) Dropwise adding the nitric acid solution prepared in the step (1) into a hydrothermal reaction kettle, wherein the adding speed of the nitric acid solution is 20-40mL/h, and the stirring speed of the reaction kettle is controlled to be 25-50r/min;
(6) When the pH value in the reaction kettle reaches 1.5-1.7, stopping adding the nitric acid solution, dropwise adding a ferric nitrate solution with the concentration of 0.1-0.5mol/L into the hydrothermal reaction kettle, wherein the adding speed of the ferric nitrate solution is 40-80mL/h, and the stirring speed of the reaction kettle is controlled to be 30-60 r/min;
(7) When the molar ratio of iron to manganese in the reaction kettle is 1;
(8) Mixing the mixed solution with an iron source, a lithium source and a carbon source to prepare a mixture with a molar ratio of Fe to Mn to Li to the carbon source =2 of (6.0-6.2) to (1.0-1.5), and carrying out spray drying on the mixture to obtain a dried material; the iron source is at least one of ferric nitrate and ferric acetate, and the lithium source is at least one of lithium acetate and lithium nitrate; the carbon source is one or two of glucose and sucrose;
(9) And calcining the dried material for 12-24h at the temperature of 600-850 ℃ under the protection of inert gas, and naturally cooling to room temperature to obtain a finished product of the ferrophosphorus lithium ion battery cathode material.
The ferrophosphorus lithium ion battery cathode material is prepared by the preparation method.
Preferably, the 0.2C discharge capacity of the ferrophosphorus lithium ion battery anode material can reach over 171.7 mAh/g.
Preferably, the 1C discharge capacity of the ferrophosphorus lithium ion battery anode material can reach more than 150.9 mAh/g.
Preferably, the capacity retention rate of the ferrophosphorus lithium ion battery cathode material after 600 times of 1C cycle can reach more than 93.93%.
The ferrophosphorus lithium ion battery cathode material is applied to the preparation of lithium ion batteries.
The invention has the beneficial effects that:
(1) According to the method, divalent manganese ions are oxidized and complexed with pyrophosphate through hydrothermal treatment to generate stable complex manganese pyrophosphate ions, and meanwhile, a water-soluble manganese salt solution is preferably a manganese nitrate solution, a water-soluble pyrophosphate solution is a tetra-ammonium pyrophosphate solution, and an acid solution is preferably a nitric acid solution, so that in the whole reaction process, the nitrate ions are continuously consumed, the final hydrothermal product only contains ferric ions, complex manganese pyrophosphate ions and nitrate ions, and impurity ions are avoided during subsequent sintering with an iron source, a lithium source and a carbon source. The reaction principle is as follows:
10Mn 2+ +2NO 3 - +30P 2 O 7 4- +72H + →10[Mn(H 2 P 2 O 7 ) 3 ] 3- +N 2 ↑+6H 2 O
NH 4 + +NO 3 - →N 2 O↑+2H 2 O；
(2) In the subsequent mixing process, the materials are uniformly mixed in a solution form, the materials with uniform mixing of the iron, the manganese, the lithium, the phosphorus and the carbon are obtained after spray drying, the anode material obtained by subsequent sintering has better distribution of the iron, the manganese, the lithium and the phosphorus, and compared with direct sintering by a solid phase method, the elements are more uniformly mixed. Meanwhile, by adopting the method, the element proportion of iron, manganese and phosphorus meets the theoretical value, and the phenomenon of more phosphorus and less phosphorus cannot be caused;
(3) The prepared ferrophosphorus lithium ion battery anode material is lithium manganese iron pyrophosphate, and the theoretical chemical formula is Li 6 Fe 2 Mn(P 2 O 7 ) 3 Compared with the conventional lithium iron phosphate LiFePO 4 The lithium-ion battery has more lithium, can be inserted and accommodated in the charging and discharging process, and has higher charging and discharging capacity.
Drawings
Fig. 1 is an SEM image of the ferrophosphorus lithium ion battery positive electrode material prepared in example 1 of the present invention.
Detailed Description
The present invention will be further described with reference to the following specific examples.
Example 1:
a preparation method of a ferrophosphorus lithium ion battery anode material comprises the following steps:
(1) Preparing a nitric acid solution with the concentration of 0.1 mol/L;
(2) Preparing a tetraammonium pyrophosphate solution with the concentration of 1 mol/L;
(3) Preparing a manganese nitrate solution with the concentration of 1 mol/L;
(4) Mixing the solutions prepared in the steps (2) and (3) according to the molar ratio of manganese to phosphorus of 1;
(5) Dropwise adding the nitric acid solution prepared in the step (1) into a hydrothermal reaction kettle, wherein the adding speed of the nitric acid solution is 40mL/h, and the stirring speed of the reaction kettle is controlled to be 50r/min;
(6) When the pH value in the reaction kettle reaches 1.7, stopping adding the nitric acid solution, dropwise adding a ferric nitrate solution with the concentration of 0.1mol/L into the hydrothermal reaction kettle at the adding speed of 80mL/h, and controlling the stirring speed of the reaction kettle at 60r/min;
(7) When the molar ratio of iron to manganese in the reaction kettle is 1;
(8) Mixing the mixed solution with an iron source, a lithium source and a carbon source to prepare a mixture with a molar ratio of Fe to Mn to Li to the carbon source =2: 6.2; the iron source is ferric nitrate, and the lithium source is lithium acetate; the carbon source is sucrose.
(9) And calcining the dried material at 850 ℃ for 12h under the protection of inert gas, and naturally cooling to room temperature to obtain the finished product of the ferrophosphorus lithium ion battery cathode material.
The ferrophosphorus lithium ion battery cathode material is prepared by the preparation method, and an SEM image of the ferrophosphorus lithium ion battery cathode material is shown in figure 1.
Example 2:
a preparation method of a ferrophosphorus lithium ion battery anode material comprises the following steps:
(1) Preparing a nitric acid solution with the concentration of 0.3 mol/L;
(2) Preparing a tetraammonium pyrophosphate solution with the concentration of 1.5 mol/L;
(3) Preparing a manganese nitrate solution with the concentration of 1.5 mol/L;
(4) Mixing the solutions prepared in the steps (2) and (3) according to the manganese-phosphorus molar ratio of 1;
(5) Dropwise adding the nitric acid solution prepared in the step (1) into a hydrothermal reaction kettle, wherein the adding speed of the nitric acid solution is 30mL/h, and the stirring speed of the reaction kettle is controlled to be 40r/min;
(6) When the pH value in the reaction kettle reaches 1.6, stopping adding the nitric acid solution, dropwise adding a ferric nitrate solution with the concentration of 0.3mol/L into the hydrothermal reaction kettle, wherein the adding speed of the ferric nitrate solution is 60mL/h, and controlling the stirring speed of the reaction kettle to be 45r/min;
(7) When the molar ratio of iron to manganese in the reaction kettle is 1;
(8) Mixing the mixed solution with an iron source, a lithium source and a carbon source to prepare a mixture with a molar ratio of Fe to Mn to Li to the carbon source = 2; the iron source is iron acetate, and the lithium source is lithium nitrate; the carbon source is glucose.
(9) And calcining the dried material for 18h at 750 ℃ under the protection of inert gas, and naturally cooling to room temperature to obtain a finished product of the ferrophosphorus lithium ion battery cathode material.
A ferrophosphorus lithium ion battery anode material is prepared by the preparation method.
Example 3:
a preparation method of a ferrophosphorus lithium ion battery anode material comprises the following steps:
(1) Preparing a nitric acid solution with the concentration of 0.5 mol/L;
(2) Preparing a tetraammonium pyrophosphate solution with the concentration of 2.0 mol/L;
(3) Preparing a manganese nitrate solution with the concentration of 2.0 mol/L;
(4) Mixing the solutions prepared in the steps (2) and (3) according to the manganese-phosphorus molar ratio of 1;
(5) Dropwise adding the nitric acid solution prepared in the step (1) into a hydrothermal reaction kettle, wherein the adding speed of the nitric acid solution is 20mL/h, and the stirring speed of the reaction kettle is controlled to be 25r/min;
(6) When the pH value in the reaction kettle reaches 1.5, stopping adding the nitric acid solution, dropwise adding a ferric nitrate solution with the concentration of 0.5mol/L into the hydrothermal reaction kettle, wherein the adding speed of the ferric nitrate solution is 40mL/h, and controlling the stirring speed of the reaction kettle to be 30r/min;
(7) When the molar ratio of iron to manganese in the reaction kettle is 1;
(8) Mixing the mixed solution with an iron source, a lithium source and a carbon source to prepare a mixture with a molar ratio of Fe to Mn to Li to the carbon source = 2; the iron source is iron acetate, and the lithium source is lithium acetate; the carbon source is glucose.
(9) And calcining the dried material for 24 hours at 600 ℃ under the protection of inert gas, and naturally cooling to room temperature to obtain the finished product of the ferrophosphorus lithium ion battery cathode material.
A ferrophosphorus lithium ion battery anode material is prepared by the preparation method.
Comparative example 1: (difference from example 1 in that no nitric acid solution was added)
A preparation method of a ferrophosphorus lithium ion battery anode material comprises the following steps:
(1) Preparing a tetraammonium pyrophosphate solution with the concentration of 1 mol/L;
(2) Preparing a manganese nitrate solution with the concentration of 1 mol/L;
(3) Mixing the solutions prepared in the steps (2) and (3) according to a manganese-phosphorus molar ratio of 1;
(4) Dropwise adding a ferric nitrate solution with the concentration of 0.1mol/L into a hydrothermal reaction kettle, wherein the adding speed of the ferric nitrate solution is 80mL/h, and the stirring speed of the reaction kettle is controlled to be 60r/min;
(5) When the molar ratio of iron to manganese in the reaction kettle is 1;
(6) Mixing the mixed solution with an iron source, a lithium source and a carbon source to prepare a mixture with a molar ratio of Fe to Mn to Li to the carbon source =2: 6.2; the iron source is ferric nitrate, and the lithium source is lithium acetate; the carbon source is sucrose.
(7) And calcining the dried material at 850 ℃ for 12h under the protection of inert gas, and naturally cooling to room temperature to obtain the finished product of the ferrophosphorus lithium ion battery cathode material.
A ferrophosphorus lithium ion battery anode material is prepared by the preparation method.
Comparative example 2: (difference from example 2 in that no nitric acid solution was added)
A preparation method of a ferrophosphorus lithium ion battery anode material comprises the following steps:
(1) Preparing a tetraammonium pyrophosphate solution with the concentration of 1.5 mol/L;
(2) Preparing a manganese nitrate solution with the concentration of 1.5 mol/L;
(3) Mixing the solutions prepared in the steps (2) and (3) according to the manganese-phosphorus molar ratio of 1;
(4) Dropwise adding a ferric nitrate solution with the concentration of 0.3mol/L into a hydrothermal reaction kettle, wherein the adding speed of the ferric nitrate solution is 60mL/h, and the stirring speed of the reaction kettle is controlled to be 45r/min;
(5) When the molar ratio of iron to manganese in the reaction kettle is 1;
(6) Mixing the mixed solution with an iron source, a lithium source and a carbon source to prepare a mixture with a molar ratio of Fe to Mn to Li to the carbon source = 2; the iron source is iron acetate, and the lithium source is lithium nitrate; the carbon source is glucose.
(7) And calcining the dried material for 18h at 750 ℃ under the protection of inert gas, and naturally cooling to room temperature to obtain a finished product of the ferrophosphorus lithium ion battery cathode material.
The ferrophosphorus lithium ion battery cathode material is prepared by the preparation method.
Comparative example 3: (difference from example 3 in that no nitric acid solution was added)
A preparation method of a ferrophosphorus lithium ion battery anode material comprises the following steps:
(1) Preparing a tetraammonium pyrophosphate solution with the concentration of 2.0 mol/L;
(2) Preparing a manganese nitrate solution with the concentration of 2.0 mol/L;
(3) Mixing the solutions prepared in the steps (2) and (3) according to the manganese-phosphorus molar ratio of 1;
(4) Dropwise adding a ferric nitrate solution with the concentration of 0.5mol/L into a hydrothermal reaction kettle, wherein the adding speed of the ferric nitrate solution is 40mL/h, and the stirring speed of the reaction kettle is controlled to be 30r/min;
(5) When the molar ratio of iron to manganese in the reaction kettle is 1;
(6) Mixing the mixed solution with an iron source, a lithium source and a carbon source to prepare a mixture with a molar ratio of Fe to Mn to Li to the carbon source = 2; the iron source is iron acetate, and the lithium source is lithium acetate; the carbon source is glucose.
(7) And calcining the dried material for 24 hours at the temperature of 600 ℃ under the protection of inert gas, and naturally cooling to room temperature to obtain a finished product of the ferrophosphorus lithium ion battery cathode material.
The ferrophosphorus lithium ion battery cathode material is prepared by the preparation method.
Comparative example 4:
mixing iron acetate, manganese acetate, tetra-ammonium pyrophosphate, lithium acetate and sucrose according to a molar ratio of Fe to Mn to P to Li to a carbon source =2 of 6.2.
The ferrophosphorus lithium ion battery cathode material is prepared by the preparation method.
Test examples:
1. the atomic percentages of the elements in any 3-point region (area: 0.5 μm by 0.5 μm) of the ferrophosphorus lithium ion battery positive electrode material finished products obtained in examples 1 to 3 and comparative examples 1 to 4 were measured by EDS, and the results are shown in table 1:
table 1. Atomic percent test results:
as can be seen from Table 1, the element distributions of examples 1 to 3 and comparative examples 1 to 3 are relatively uniform, and the element distribution of comparative example 4 is not uniform.
2. Mixing the finished product of the ferrophosphorus lithium ion battery anode material obtained in the embodiment and the comparative example, acetylene black as a conductive agent and PVDF as a binder according to a mass ratio of 8; the diaphragm is Celgard2400 polypropylene porous membrane; the solvent in the electrolyte is a solution composed of EC, DMC and EMC according to a mass ratio of 1 6 ，LiPF 6 The concentration of (b) is 1.0mol/L; a 2023 button cell battery was assembled in a glove box. Carrying out charge-discharge cycle performance test on the battery, and testing the discharge specific capacity of 0.2C and 1C within the range of cut-off voltage of 2.2-4.3V; the results of testing electrochemical performance are shown in table 2 below.
Table 2 electrochemical performance test results:
as can be seen from Table 2, the 0.2C discharge capacity of the ferrophosphorus lithium ion battery anode material prepared by the preparation method can reach over 171.7mAh/g, the 1C discharge capacity can reach over 150.9mAh/g, and the capacity retention rate after 1C circulation for 600 times can reach over 93.93%.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. A preparation method of a ferrophosphorus lithium ion battery anode material is characterized by comprising the following steps: the method comprises the following steps:
(1) Mixing a water-soluble manganese salt solution and a water-soluble pyrophosphate solution, adding an acid solution to adjust the pH value to be acidic, and then adding a water-soluble iron salt solution to react to obtain a mixed solution;
(2) Mixing the mixed solution obtained in the step (1) with an iron source, a lithium source and a carbon source to obtain a mixture, and drying to obtain a dried material;
(3) And (3) calcining the dried material obtained in the step (2) in inert gas to obtain the ferrophosphorus lithium ion battery anode material.
2. The preparation method of the ferrophosphorus lithium ion battery cathode material according to claim 1, wherein the preparation method comprises the following steps: in the step (1), the water-soluble manganese salt solution is a manganese nitrate solution, the water-soluble pyrophosphate solution is a tetra-ammonium pyrophosphate solution, and the acid solution is a nitric acid solution.
3. The preparation method of the ferrophosphorus lithium ion battery cathode material according to claim 1, wherein the preparation method comprises the following steps: in the step (1), the water-soluble manganese salt solution and the water-soluble pyrophosphate solution are mixed according to the manganese-phosphorus molar ratio of 1 (2-5).
4. The preparation method of the ferrophosphorus lithium ion battery cathode material according to claim 1, wherein the preparation method comprises the following steps: in the step (1), the pH adjustment to be acidic means that the pH is adjusted to 1.0-3.0.
5. The preparation method of the ferrophosphorus lithium ion battery cathode material according to claim 1, wherein the preparation method comprises the following steps: in the step (1), the water-soluble iron salt solution is added dropwise under stirring, the adding speed is 30-100mL/h, and the stirring speed is 20-100r/min.
6. The preparation method of the ferrophosphorus lithium ion battery cathode material according to claim 1, wherein the preparation method comprises the following steps: in the step (2), the ratio of Fe, mn, li and the carbon source =2 in the mixture is (6.0-6.5) and (1.0-2.0).
7. The preparation method of the ferrophosphorus lithium ion battery cathode material according to claim 1, wherein the preparation method comprises the following steps: in the step (2), the drying mode is spray drying.
8. The preparation method of the ferrophosphorus lithium ion battery cathode material according to claim 1, wherein the preparation method comprises the following steps: in the step (3), the calcining temperature is 500-1000 ℃, and the calcining time is 10-30h.
9. The ferrophosphorus lithium ion battery cathode material is characterized in that: prepared by the preparation method of any one of claims 1 to 8.
10. The use of the ferrophosphorus lithium ion battery cathode material of claim 9 in the preparation of a lithium ion battery.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211107860.6A CN115432685B (en) | 2022-09-13 | 2022-09-13 | Ferrophosphorus lithium ion battery positive electrode material, and preparation method and application thereof |
| PCT/CN2023/077683 WO2024055517A1 (en) | 2022-09-13 | 2023-02-22 | Ferrophosphorus lithium-ion battery positive electrode material, and preparation method therefor and use thereof |
| FR2306739A FR3139669A1 (en) | 2022-09-13 | 2023-06-27 | LITHIUM-ION IRON-PHOSPHORUS BATTERY CATHODE MATERIAL, PREPARATION METHOD AND USE OF THIS MATERIAL TECHNICAL FIELD |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211107860.6A CN115432685B (en) | 2022-09-13 | 2022-09-13 | Ferrophosphorus lithium ion battery positive electrode material, and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115432685A true CN115432685A (en) | 2022-12-06 |
| CN115432685B CN115432685B (en) | 2024-01-05 |
Family
ID=84245958
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211107860.6A Active CN115432685B (en) | 2022-09-13 | 2022-09-13 | Ferrophosphorus lithium ion battery positive electrode material, and preparation method and application thereof |
Country Status (3)
| Country | Link |
|---|---|
| CN (1) | CN115432685B (en) |
| FR (1) | FR3139669A1 (en) |
| WO (1) | WO2024055517A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2024055517A1 (en) * | 2022-09-13 | 2024-03-21 | 广东邦普循环科技有限公司 | Ferrophosphorus lithium-ion battery positive electrode material, and preparation method therefor and use thereof |
| WO2024120363A1 (en) * | 2022-12-08 | 2024-06-13 | 北京林立新能源有限公司 | Method for preparing manganese phosphate |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090220858A1 (en) * | 2008-02-29 | 2009-09-03 | Byd Company Limited | Composite Compound With Mixed Crystalline Structure |
| US20150072238A1 (en) * | 2013-09-04 | 2015-03-12 | Lg Chem, Ltd. | Transition metal- pyrophosphate anode active material, method of preparing the same, and lithium secondary battery or hybrid capacitor including the anode active material |
| US20160013474A1 (en) * | 2013-03-04 | 2016-01-14 | Suzhou Institute Of Nano-Tech And Nano-Bionics Of Chinese Academy Of Sciences | Porous Lithium Mangaense Phosphate-Carbon Composite Material, Preparation Method and Application Thereof |
| CN105355885A (en) * | 2015-11-26 | 2016-02-24 | 中南大学 | Synthesis method of lithium ion battery composite cathode material LiMn1-xFexPO4/C |
| CN105702954A (en) * | 2014-11-26 | 2016-06-22 | 比亚迪股份有限公司 | Positive electrode material LiMn1-xFexPO4 / C and preparation method thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102779995A (en) * | 2011-05-13 | 2012-11-14 | 上海空间电源研究所 | Phosphoric acid cathode material of lithium battery |
| CN104037413A (en) * | 2014-06-19 | 2014-09-10 | 合肥国轩高科动力能源股份公司 | Preparation method of positive electrode material (carbon-coated iron-manganese-lithium phosphate) of lithium ion battery |
| CN113659134A (en) * | 2021-07-09 | 2021-11-16 | 江苏乐能电池股份有限公司 | Method for preparing nanoscale lithium manganese iron phosphate material by using co-crystallization method |
| CN115432685B (en) * | 2022-09-13 | 2024-01-05 | 广东邦普循环科技有限公司 | Ferrophosphorus lithium ion battery positive electrode material, and preparation method and application thereof |
-
2022
- 2022-09-13 CN CN202211107860.6A patent/CN115432685B/en active Active
-
2023
- 2023-02-22 WO PCT/CN2023/077683 patent/WO2024055517A1/en unknown
- 2023-06-27 FR FR2306739A patent/FR3139669A1/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090220858A1 (en) * | 2008-02-29 | 2009-09-03 | Byd Company Limited | Composite Compound With Mixed Crystalline Structure |
| US20160013474A1 (en) * | 2013-03-04 | 2016-01-14 | Suzhou Institute Of Nano-Tech And Nano-Bionics Of Chinese Academy Of Sciences | Porous Lithium Mangaense Phosphate-Carbon Composite Material, Preparation Method and Application Thereof |
| US20150072238A1 (en) * | 2013-09-04 | 2015-03-12 | Lg Chem, Ltd. | Transition metal- pyrophosphate anode active material, method of preparing the same, and lithium secondary battery or hybrid capacitor including the anode active material |
| CN105702954A (en) * | 2014-11-26 | 2016-06-22 | 比亚迪股份有限公司 | Positive electrode material LiMn1-xFexPO4 / C and preparation method thereof |
| CN105355885A (en) * | 2015-11-26 | 2016-02-24 | 中南大学 | Synthesis method of lithium ion battery composite cathode material LiMn1-xFexPO4/C |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2024055517A1 (en) * | 2022-09-13 | 2024-03-21 | 广东邦普循环科技有限公司 | Ferrophosphorus lithium-ion battery positive electrode material, and preparation method therefor and use thereof |
| WO2024120363A1 (en) * | 2022-12-08 | 2024-06-13 | 北京林立新能源有限公司 | Method for preparing manganese phosphate |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115432685B (en) | 2024-01-05 |
| FR3139669A1 (en) | 2024-03-15 |
| WO2024055517A1 (en) | 2024-03-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US10957903B2 (en) | Layered lithium-rich manganese-based cathode material with olivine structured LIMPO4 surface modification and preparation method thereof | |
| CA2623636C (en) | Method of producing positive electrode active material and nonaqueous electrolyte battery using same | |
| CN115432685B (en) | Ferrophosphorus lithium ion battery positive electrode material, and preparation method and application thereof | |
| WO2022048346A1 (en) | Vanadium pentoxide/rgo-coated lithium nickel cobalt manganese oxide positive electrode material and preparation method therefor | |
| CN109786701B (en) | Modified LiNi0.8Co0.1Mn0.1O2Preparation method of ternary cathode material, product and battery | |
| CN111082009B (en) | Lithium-rich manganese-based composite positive electrode material improved by adopting phosphate and preparation method thereof | |
| CN110660978B (en) | Lithium ion battery positive electrode material with core-shell structure and preparation method thereof, positive plate, lithium ion battery and application thereof | |
| CN115477295B (en) | Method for preparing lithium iron manganese phosphate anode material by spray combustion and application thereof | |
| CN111009645A (en) | graphene-based/AlPO4Method for compositely coating modified high-nickel ternary cathode material | |
| CN105576236A (en) | Lithium ion battery 442 ternary anode modified material and preparing method thereof | |
| CN115520846A (en) | Preparation method and application of lithium iron manganese phosphate | |
| CN101651198B (en) | Doping lithium iron phosphate material and preparation method and application thereof | |
| CN101209819B (en) | Method for preparing lithium iron phosphate | |
| CN115611773B (en) | Lithium supplementing compound, preparation method thereof and lithium ion battery | |
| CN114933292B (en) | Preparation method and application of lithium iron phosphate | |
| CN114864894B (en) | High-pressure-resistant coating modified lithium-rich manganese-based positive electrode material and preparation method and application thereof | |
| CN113745514B (en) | Fluorine-doped and lithium silicate-coated lithium-rich manganese-based positive electrode material and preparation method and application thereof | |
| CN112436135B (en) | Cathode material and preparation method and application thereof | |
| CN114649526A (en) | Lithium-rich manganese-based layered material with high inner part and low outer part gradient doping and preparation method thereof | |
| CN114864945A (en) | Preparation method and application of high-conductivity lithium iron phosphate | |
| CN113764671A (en) | Anode material of lithium ion battery | |
| CN113130900A (en) | Vanadium pentoxide-coated high-nickel ternary lithium ion battery positive electrode material and preparation method thereof | |
| CN106450232B (en) | preparation method and application of novel lithium ion battery anode material ternary phosphate | |
| CN115275170B (en) | Preparation method of cerium dioxide modified lithium iron manganese phosphate electrode material | |
| CN110098405B (en) | Preparation method of anode material for lithium ion battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |