WO2023124575A1 - 一种锂离子电池正极材料及其制备方法 - Google Patents
一种锂离子电池正极材料及其制备方法 Download PDFInfo
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- WO2023124575A1 WO2023124575A1 PCT/CN2022/131292 CN2022131292W WO2023124575A1 WO 2023124575 A1 WO2023124575 A1 WO 2023124575A1 CN 2022131292 W CN2022131292 W CN 2022131292W WO 2023124575 A1 WO2023124575 A1 WO 2023124575A1
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- lithium
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- suspension
- manganese
- ion battery
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 49
- 239000000725 suspension Substances 0.000 claims abstract description 48
- DVATZODUVBMYHN-UHFFFAOYSA-K lithium;iron(2+);manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[Fe+2].[O-]P([O-])([O-])=O DVATZODUVBMYHN-UHFFFAOYSA-K 0.000 claims abstract description 47
- 239000000463 material Substances 0.000 claims abstract description 41
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000008367 deionised water Substances 0.000 claims abstract description 31
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 31
- 239000011572 manganese Substances 0.000 claims abstract description 26
- 239000011259 mixed solution Substances 0.000 claims abstract description 23
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 19
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 18
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052742 iron Inorganic materials 0.000 claims abstract description 18
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 18
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 18
- 239000011574 phosphorus Substances 0.000 claims abstract description 18
- 239000000243 solution Substances 0.000 claims abstract description 17
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 10
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims abstract description 9
- 239000002105 nanoparticle Substances 0.000 claims abstract description 4
- 239000000047 product Substances 0.000 claims description 28
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical group [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 24
- 239000010406 cathode material Substances 0.000 claims description 20
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 16
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 13
- 238000000137 annealing Methods 0.000 claims description 11
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 10
- 235000006708 antioxidants Nutrition 0.000 claims description 9
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 8
- 239000011668 ascorbic acid Substances 0.000 claims description 8
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 6
- 239000011790 ferrous sulphate Substances 0.000 claims description 6
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 6
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 6
- 229940071125 manganese acetate Drugs 0.000 claims description 6
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 6
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 5
- 229910002651 NO3 Inorganic materials 0.000 claims description 5
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 5
- 229960005070 ascorbic acid Drugs 0.000 claims description 5
- 235000010323 ascorbic acid Nutrition 0.000 claims description 5
- 229940099596 manganese sulfate Drugs 0.000 claims description 5
- 235000007079 manganese sulphate Nutrition 0.000 claims description 5
- 239000011702 manganese sulphate Substances 0.000 claims description 5
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 5
- 238000005119 centrifugation Methods 0.000 claims description 4
- 229960002089 ferrous chloride Drugs 0.000 claims description 4
- 229940062993 ferrous oxalate Drugs 0.000 claims description 4
- 239000012467 final product Substances 0.000 claims description 4
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 4
- OWZIYWAUNZMLRT-UHFFFAOYSA-L iron(2+);oxalate Chemical compound [Fe+2].[O-]C(=O)C([O-])=O OWZIYWAUNZMLRT-UHFFFAOYSA-L 0.000 claims description 4
- 235000006748 manganese carbonate Nutrition 0.000 claims description 4
- 239000011656 manganese carbonate Substances 0.000 claims description 4
- 229940093474 manganese carbonate Drugs 0.000 claims description 4
- RGVLTEMOWXGQOS-UHFFFAOYSA-L manganese(2+);oxalate Chemical compound [Mn+2].[O-]C(=O)C([O-])=O RGVLTEMOWXGQOS-UHFFFAOYSA-L 0.000 claims description 4
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 claims description 4
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 claims description 4
- 230000001681 protective effect Effects 0.000 claims description 4
- 150000002500 ions Chemical class 0.000 abstract description 9
- 238000001035 drying Methods 0.000 abstract description 2
- 230000005540 biological transmission Effects 0.000 abstract 1
- 238000005245 sintering Methods 0.000 abstract 1
- 238000005406 washing Methods 0.000 abstract 1
- 239000011248 coating agent Substances 0.000 description 9
- 238000000576 coating method Methods 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 5
- 229910015645 LiMn Inorganic materials 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 229910021389 graphene Inorganic materials 0.000 description 4
- 229960001781 ferrous sulfate Drugs 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 2
- QSNQXZYQEIKDPU-UHFFFAOYSA-N [Li].[Fe] Chemical compound [Li].[Fe] QSNQXZYQEIKDPU-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 229920001940 conductive polymer Polymers 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- CPSYWNLKRDURMG-UHFFFAOYSA-L hydron;manganese(2+);phosphate Chemical compound [Mn+2].OP([O-])([O-])=O CPSYWNLKRDURMG-UHFFFAOYSA-L 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- AWKHTBXFNVGFRX-UHFFFAOYSA-K iron(2+);manganese(2+);phosphate Chemical compound [Mn+2].[Fe+2].[O-]P([O-])([O-])=O AWKHTBXFNVGFRX-UHFFFAOYSA-K 0.000 description 2
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- -1 specifically Substances 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229910000616 Ferromanganese Inorganic materials 0.000 description 1
- 229910016096 LiMn0.5Fe0.5PO4 Inorganic materials 0.000 description 1
- 229910014985 LiMnxFe1-xPO4 Inorganic materials 0.000 description 1
- 229910014982 LiMnxFe1−xPO4 Inorganic materials 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical compound [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000010450 olivine Substances 0.000 description 1
- 229910052609 olivine Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
Images
Classifications
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- 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
-
- 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
-
- 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
-
- 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
Definitions
- the invention belongs to the technical field of new energy materials and their preparation, and in particular relates to a lithium-ion battery positive electrode material of Ti3C2MXene -coated lithium manganese iron phosphate material and a preparation method thereof.
- the material can be used as a high - performance positive electrode material in lithium-ion batteries. battery application.
- Olivine-type lithium iron phosphate (LiFePO 4 ) is one of the cathode materials for lithium-ion batteries that have been successfully commercialized.
- the advantages of high safety, long cycle life and low cost have made its market share in the power battery cathode material market continue to increase. .
- the low specific capacity and working voltage (3.45Vvs.Li/Li + ) make it difficult to further improve the energy density of LiFePO 4 power batteries.
- Lithium manganese iron phosphate (LiMn x Fe 1-x PO 4 ) has an olivine structure similar to LiFePO 4 , its operating voltage reaches 4.10V, and its energy density is about 20% higher than that of LiFePO 4 .
- LiMn x Fe 1-x PO 4 cathode materials it is of great significance to develop high-performance LiMn x Fe 1-x PO 4 cathode materials to replace LiFePO 4 cathode materials for improving the energy density of power batteries.
- the lower electron conduction and ion diffusion rates lead to poor high-current charge-discharge performance of LiMnxFe1 - xPO4 .
- the poor structural stability of this material reduces its electrochemical cycling stability and limits its practical application.
- LiMn x Fe 1-x PO 4 Surface coating of LiMn x Fe 1-x PO 4 with highly conductive materials can effectively improve its ion and electron transport capabilities, thereby achieving good electrochemical performance.
- Common high-conductivity materials used for LiMn x Fe 1-x PO 4 coating include amorphous carbon, graphene, and conductive polymers.
- the Chinese invention patent (CN109244391B) discloses a nitrogen-doped carbon-coated lithium manganese iron phosphate material and its preparation method.
- the nitrogen-doped carbon-doped lithium manganese iron phosphate material prepared by the invention has good conductivity, high specific capacity, and has The advantages of good low temperature resistance and high magnification.
- the Chinese invention patent introduces a preparation method of a conductive polymer-coated lithium manganese iron phosphate cathode material.
- the invention effectively improves the LiMn x Fe 1-x PO 4 by coating the polyaniline surface. Electrochemical performance of 1-x PO4 .
- the paper J. Power Sources, 329 (2016) 94
- the paper reported that the LiMn 0.5 Fe 0.5 PO 4 cathode material was coated with graphene as the carbon source, and the continuous graphene sheets connected the particles with a size of 20nm to form a stable Conductive network, the specific discharge capacity of the product can reach 166 and 90mAh g –1 at 0.1C and 20C rates, respectively.
- the surface coating of the above conductive materials can enhance the conductivity of lithium manganese iron phosphate to a certain extent, the interaction and affinity between these materials and lithium manganese iron phosphate are poor, and the rate performance and structure of lithium manganese iron phosphate cannot be fully improved. stability.
- Ti 3 C 2 MXene is a new type of two-dimensional material, which has a structure similar to graphene, high electrical conductivity, abundant surface functional groups and good mechanical properties.
- the present invention aims at the above defects and improvement needs in the prior art, and proposes a method to effectively improve the ion and electron transport capacity and structural stability of lithium manganese iron phosphate material through the surface coating of Ti 3 C 2 MXene, so as to obtain a high Lithium-ion battery cathode material with electrochemical performance and preparation method thereof.
- the anode material of the lithium ion battery mentioned above is Ti 3 C 2 MXene coated lithium manganese iron phosphate material, specifically, Ti 3 C 2 MXene is uniformly coated on the surface of lithium manganese iron phosphate nanoparticles to form a conductive network.
- the preparation method of the lithium-ion battery cathode material is to add phosphorus source and lithium source to deionized water/PEG solution to form suspension A, and add manganese source, iron source, antioxidant and Ti3C2MXene to deionized water
- To form suspension B add suspension B dropwise to suspension A under continuous stirring conditions to form a mixed solution, then transfer the mixed solution to a hydrothermal reactor and keep it warm at a certain temperature for a period of time, centrifuge after the reaction is completed The product is washed and dried, and finally the dried product is sintered in an atmosphere furnace to obtain a Ti 3 C 2 MXene-coated lithium manganese iron phosphate material.
- the preparation method of described lithium-ion battery cathode material comprises the following specific steps:
- step (2) Transfer the mixed solution obtained in step (1) to a hydrothermal reaction kettle, tighten the reaction kettle and place it in an oven at a temperature of 140-200° C. for 5-20 hours;
- step (3) Annealing the dried hydrothermal product obtained in step (3) under a protective atmosphere at a temperature of 500-800° C. for 5-20 hours to obtain a Ti 3 C 2 MXene-coated lithium manganese iron phosphate material.
- the preparation method of the lithium ion battery cathode material wherein: the phosphorus source is phosphoric acid.
- the lithium source is lithium hydroxide.
- the manganese source is one or more of manganese sulfate, manganese carbonate, manganese acetate and manganese oxalate.
- the iron source is one or more of ferrous sulfate, ferrous chloride, ferrous nitrate and ferrous oxalate.
- the antioxidant is ascorbic acid.
- the volume ratio of deionized water to PEG in the deionized water/PEG solution is 5:1, 2:1 or 1:1.
- the present invention uses Ti 3 C 2 MXene with high electrical conductivity, rich surface functional groups and good mechanical properties to coat lithium manganese iron phosphate material, and designs the overall process of the preparation method, the key hydrothermal reaction and high temperature annealing process
- the parameter conditions are improved, which effectively improves the ion and electron transport capabilities of the lithium manganese iron phosphate material.
- the strong interaction between Ti 3 C 2 MXene and the lithium manganese iron phosphate material can improve the structural stability of the lithium manganese iron phosphate material.
- the obtained Ti 3 C 2 MXene-coated lithium manganese iron phosphate cathode material has an initial discharge capacity of 157.4mAh g –1 at 0.1C.
- the present invention uses Ti 3 C 2 MXene to coat the surface of the lithium manganese iron phosphate material, it can effectively improve the ion and electron transport capacity and structural stability of the lithium manganese iron phosphate material, and Ti 3 C 2 MXene coats the lithium manganese iron phosphate material
- the discharge capacity of the positive electrode material at 0.1C is 157.4mAh g -1 , and the discharge capacity at 1C reaches 145.0mAh g -1 , which is very suitable as a high energy and high power density lithium ion battery positive electrode material.
- Figure 1 is the XRD spectrum of lithium manganese iron phosphate and Ti 3 C 2 MXene coated lithium manganese iron phosphate;
- Figure 2 (a) SEM image of lithium manganese iron phosphate; (b) SEM image of Ti 3 C 2 MXene coated lithium manganese iron phosphate;
- Figure 3 is the first charge and discharge diagram of lithium manganese iron phosphate and Ti 3 C 2 MXene coated lithium manganese iron phosphate.
- the positive electrode material of the lithium ion battery of the present invention is Ti 3 C 2 MXene coated manganese iron phosphate material, specifically, Ti 3 C 2 MXene is evenly coated on the surface of lithium manganese iron phosphate nanoparticles to form a conductive network, and Ti 3 C 2 MXene coating lithium manganese iron phosphate effectively improves the ion and electron transport capacity and structural stability of lithium manganese iron phosphate.
- the preparation method of the Ti 3 C 2 MXene-coated manganese iron phosphate material of the positive electrode material of lithium ion battery of the present invention is to add phosphorus source and lithium source to deionized water/PEG solution to form suspension A, manganese source, iron source, Antioxidants and Ti 3 C 2 MXene were added to deionized water to form a suspension B, and the suspension B was added dropwise to the suspension A under continuous stirring to form a mixed solution, and then the mixed solution was transferred to a hydrothermal reaction kettle for Keeping at a certain temperature for a period of time, after the reaction is completed, the product is centrifuged and washed and dried, and finally the dried product is sintered in an atmosphere furnace to obtain a Ti 3 C 2 MXene-coated lithium manganese iron phosphate material.
- the method includes the following specific steps:
- step (2) Transfer the mixed solution obtained in step (1) to a hydrothermal reaction kettle, tighten the reaction kettle and place it in an oven at a temperature of 140-200° C. for 5-20 hours;
- step (3) Annealing the dried hydrothermal product obtained in step (3) under a protective atmosphere at a temperature of 500-800° C. for 5-20 hours to obtain a Ti 3 C 2 MXene-coated lithium manganese iron phosphate material.
- the phosphorus source is phosphoric acid;
- the lithium source is lithium hydroxide;
- the manganese source is one or more of manganese sulfate, manganese carbonate, manganese acetate and manganese oxalate;
- the iron source is ferrous sulfate, chlorine One or more in ferrous chloride, ferrous nitrate and ferrous oxalate;
- Antioxidant is ascorbic acid; In deionized water/PEG solution, the volume ratio of deionized water and PEG is 5:1, 2:1 or 1: 1.
- the protective atmosphere in step (4) is 95vol% Ar+5vol% H 2 .
- the volume ratio of deionized water to PEG in the deionized water/PEG solution described in step (1) is more preferably 2:1.
- the amount of Ti 3 C 2 MXene added in step (1) is more preferably 15wt% in the final product.
- the holding temperature in step (2) is 180° C.
- the holding time is 10 hours.
- the drying temperature in step (3) is more preferably 60°C.
- the annealing temperature in step (4) is 650° C., and the annealing time is 10 h.
- the present invention effectively enhances the ion and electron transport capacity and structural stability of lithium iron phosphate by coating lithium manganese iron phosphate with Ti 3 C 2 MXene, so that the material has outstanding electrochemical properties, and the obtained Ti 3 C
- the initial discharge capacity of 2 MXene-coated lithium manganese iron phosphate material is 157.4mAh g –1 at 0.1C, the first Coulombic efficiency is higher than 99%, and the discharge capacity at 1C reaches 145.0mAh g –1 .
- a black powder of Ti 3 C 2 MXene-coated manganese phosphate can be obtained Lithium iron material; the content of Ti 3 C 2 MXene in this product is 15wt%, its initial discharge capacity is 157.4mAh g –1 , and its initial coulombic efficiency is 99.6%.
- the hydrothermal product is centrifuged and washed. Dry at 80°C under vacuum; finally, anneal the dried hydrothermal product at 500°C for 20 hours in an atmosphere of 95vol% Ar+5vol% H 2 .
- black powder Ti 3 C 2 MXene coated manganese phosphate can be obtained Lithium iron material; the content of Ti 3 C 2 MXene in this product is 5wt%, its initial discharge capacity is 130.4mAh g –1 , and its initial coulombic efficiency is 95.6%.
- the present invention also uses uncoated lithium manganese iron phosphate material, that is, compared with the uncoated lithium manganese iron phosphate material that does not add Ti 3 C 2 MXene during the preparation process, see Figure 1, Figure 2, Figure 3, It is not difficult to find from these figures that Ti 3 C 2 MXene surface coating can effectively enhance the electrochemical performance of lithium manganese iron phosphate material, and a lithium-ion battery cathode material with high energy and power density can be obtained.
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- Chemical Kinetics & Catalysis (AREA)
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- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
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Abstract
本发明涉及一种锂离子电池正极材料及其制备方法,该正极材料为Ti 3C 2MXene包覆磷酸锰铁锂材料,是将Ti 3C 2MXene均匀地包覆在磷酸锰铁锂纳米颗粒表面并形成导电网络。其制备方法是将磷源和锂源加入去离子水/PEG溶液中形成悬浮液A,锰源、铁源、抗氧化剂和Ti 3C 2MXene加入去离子水中形成悬浮液B,在持续搅拌条件下将悬浮液B滴加到悬浮液A中形成混合液,再将此混合液转移到水热反应釜中保温,反应完成后离心分离出产物洗涤烘干后烧结得到。本发明使用Ti 3C 2MXene对磷酸锰铁锂材料进行表面包覆,有效地提高磷酸锰铁锂材料离子和电子传输能力以及结构稳定性,非常适用于作为高能量和高功率密度锂离子电池正极材料。
Description
本申请要求于2021年12月29日提交中国专利局、申请号为202111631871.X、发明名称为“一种锂离子电池正极材料及其制备方法”的中国专利申请的优先权,其全部内容通过引用结合在本申请中。
本发明属于新能源材料及其制备技术领域,具体涉及一种Ti
3C
2 MXene包覆磷酸锰铁锂材料的锂离子电池正极材料及其制备方法,该材料可作为高性能正极材料在锂离子电池中应用。
橄榄石型磷酸铁锂(LiFePO
4)是成功实现商业化应用的锂离子电池正极材料之一,高安全性、长循环寿命和低成本等优势使得其在动力电池正极材料市场的占比不断提升。然而,较低的比容量和工作电压(3.45Vvs.Li/Li
+)导致LiFePO
4动力电池的能量密度难以得到进一步提升。磷酸锰铁锂(LiMn
xFe
1-xPO
4)具有与LiFePO
4相似的橄榄石结构,其工作电压达到4.10V,能量密度相较于LiFePO
4的能量密度提高20%左右。因此,开发高性能的LiMn
xFe
1-xPO
4正极材料取代LiFePO
4正极材料,对于提升动力电池的能量密度具有十分重要的意义。然而,较低的电子传导和离子扩散速率导致LiMn
xFe
1-xPO
4的大电流充放电性能较差。此外,该材料的结构稳定性较差,降低了其电化学循环稳定性,限制了其实际应用。
使用高导电性材料对LiMn
xFe
1-xPO
4进行表面包覆可以有效提高其离子和电子传输能力,从而实现良好的电化学性能。常见的用于LiMn
xFe
1-xPO
4包覆的高导电性材料有无定形碳、石墨烯和导电高分子等。如中国发明专利(CN109244391B)公开了一种氮掺杂碳包覆磷酸锰铁锂材料及其制备方法,该发明制备的氮掺杂碳磷酸锰铁锂材料的导电性好、比容量高,具有耐低温性能好和倍率高的优点。中国发明专利(CN113066969A)介绍了一种导电高分子包覆磷酸锰铁锂正极材料的制备方法,该发明通过对LiMn
xFe
1-xPO
4进行聚苯胺表面包覆,有效提高了LiMn
xFe
1-xPO
4的电化学性能。论文(J.Power Sources,329(2016)94)报道了以石墨烯为碳源对LiMn
0.5Fe
0.5PO
4正极材料进行包覆, 连续的石墨烯片将尺寸为20nm的颗粒连接起来形成稳定的导电网络,产物在0.1C和20C倍率下放电比容量分别可以达到166和90mAh g
–1。以上导电材料的表面包覆虽然可以在一定程度上增强磷酸锰铁锂的导电性,但是这些材料与磷酸锰铁锂的相互作用和亲和力较差,不能充分提高磷酸锰铁锂的倍率性能和结构稳定性。
Ti
3C
2 MXene是一种新型二维材料,具有和石墨烯类似的结构以及高导电性、丰富的表面官能团和良好的力学性能。
因此将Ti
3C
2 MXene用于电极材料的表面包覆以实现电极材料的离子和电子传输能力以及结构稳定性的优化,从而得到高性能锂离子电池正极材料是需要解决的技术问题。
发明内容
本发明针对现有技术存在的上述缺陷和改进需求,而提出一种通过Ti
3C
2MXene的表面包覆有效地提高磷酸锰铁锂材料的离子和电子传输能力以及结构稳定性从而得到具有高电化学性能的锂离子电池正极材料及其制备方法。
本发明是通过以下技术方案实现的:
上述的锂离子电池正极材料,所述材料为Ti
3C
2 MXene包覆磷酸锰铁锂材料,具体是将Ti
3C
2 MXene均匀地包覆在磷酸锰铁锂纳米颗粒表面并形成导电网络。
所述的锂离子电池正极材料的制备方法,是将磷源和锂源加入去离子水/PEG溶液中形成悬浮液A,锰源、铁源、抗氧化剂和Ti
3C
2 MXene加入去离子水中形成悬浮液B,在持续搅拌条件下将悬浮液B滴加到悬浮液A中形成混合液,再将此混合液转移到水热反应釜中于一定温度下保温一段时间,反应完成后离心分离出产物并将其洗涤烘干,最后将干燥的产物在气氛炉中进行烧结得到Ti
3C
2 MXene包覆的磷酸锰铁锂材料。
所述的锂离子电池正极材料的制备方法,包括以下具体步骤:
(1)将磷源和锂源加入去离子水/PEG溶液中形成悬浮液A;将锰源、铁源、抗氧化剂和Ti
3C
2 MXene加入去离子水中形成悬浮液B;在持续搅拌条件下将悬浮液B滴加到悬浮液A中形成混合液;其中锂源、锰源、铁源和磷源的元素摩尔比Li:Mn:Fe:P=3:1-x:x:2,0.1≤x≤0.5,Ti
3C
2 MXene的加入量应使其在 最终产物中的含量为5-30wt%;
(2)将步骤(1)得到的混合液转移到水热反应釜中,拧紧反应釜后将其置于烘箱中于140-200℃的温度条件下保温5-20h;
(3)反应完成后离心分离出水热产物并将其进行洗涤后在真空条件下温度烘干,烘干温度为30-80℃;
(4)将步骤(3)所得干燥的水热产物在保护气氛下于500-800℃的温度条件下退火5-20h,即可得到Ti
3C
2 MXene包覆磷酸锰铁锂材料。
所述的锂离子电池正极材料的制备方法,其中:所述磷源为磷酸。所述锂源为氢氧化锂。所述锰源为硫酸锰、碳酸锰、乙酸锰和草酸锰中的一种或几种。所述铁源为硫酸亚铁、氯化亚铁、硝酸亚铁和草酸亚铁中的一种或几种。所述抗氧化剂为抗坏血酸。所述去离子水/PEG溶液中去离子水与PEG的体积比为5:1、2:1或1:1。
本发明首次将具有高导电能力、丰富表面官能团和良好力学性能的Ti
3C
2MXene用于包覆磷酸锰铁锂材料,并对制备方法整体流程工艺设计,关键的水热反应和高温退火工艺的参数条件进行改进,有效地提高了磷酸锰铁锂材料的离子和电子传输能力,同时Ti
3C
2 MXene和磷酸锰铁锂材料较强的相互作用能够提升磷酸锰铁锂材料的结构稳定性,所得Ti
3C
2 MXene包覆的磷酸锰铁锂正极材料在0.1C的首次放电容量达到157.4mAh g
–1。
本发明由于使用Ti
3C
2 MXene对磷酸锰铁锂材料进行表面包覆,能有效地提高磷酸锰铁锂材料离子和电子传输能力以及结构稳定性,Ti
3C
2 MXene包覆磷酸锰铁锂正极材料在0.1C的放电容量为157.4mAh g
–1,1C的放电容量达到145.0mAh g
–1,非常适用于作为高能量和高功率密度锂离子电池正极材料。
图1为磷酸锰铁锂与Ti
3C
2 MXene包覆磷酸锰铁锂的XRD谱线图;
图2(a)磷酸锰铁锂的SEM图;(b)Ti
3C
2 MXene包覆磷酸锰铁锂的SEM图;
图3为磷酸锰铁锂与Ti
3C
2 MXene包覆磷酸锰铁锂的首次充放电图。
本发明的锂离子电池正极材料,是Ti
3C
2 MXene包覆磷酸锰铁锂材料,具体是将Ti
3C
2 MXene均匀地包覆在磷酸锰铁锂纳米颗粒表面并形成导电网络,采用Ti
3C
2 MXene包覆磷酸锰铁锂有效地提升了磷酸锰铁锂的离子和电子传输能力以及结构稳定性。
本发明锂离子电池正极材料的Ti
3C
2 MXene包覆磷酸锰铁锂材料的制备方法,是将磷源和锂源加入去离子水/PEG溶液中形成悬浮液A,锰源、铁源、抗氧化剂和Ti
3C
2 MXene加入去离子水中形成悬浮液B,在持续搅拌条件下将悬浮液B滴加到悬浮液A中形成混合液,再将此混合液转移到水热反应釜中于一定温度下保温一段时间,反应完成后离心分离出产物并将其洗涤烘干,最后将干燥的产物在气氛炉中进行烧结即可得到Ti
3C
2 MXene包覆磷酸锰铁锂材料。该方法包括以下具体步骤:
(1)将磷源和锂源加入去离子水/PEG溶液中形成悬浮液A;将锰源、铁源、抗氧化剂和Ti
3C
2 MXene加入去离子水中形成悬浮液B;在持续搅拌条件下将悬浮液B滴加到悬浮液A中形成混合液;其中锂源、锰源、铁源和磷源的元素摩尔比Li:Mn:Fe:P=3:1-x:x:2,0.1≤x≤0.5,Ti
3C
2 MXene的加入量应使其在最终产物中的含量为5-30wt%;
(2)将步骤(1)得到的混合液转移到水热反应釜中,拧紧反应釜后将其置于烘箱中于140-200℃的温度条件下保温5-20h;
(3)反应完成后离心分离出水热产物并将其进行洗涤后在真空条件下温度烘干,烘干温度为30-80℃;
(4)将步骤(3)所得干燥的水热产物在保护气氛下于500-800℃的温度条件下退火5-20h,即可得到Ti
3C
2 MXene包覆磷酸锰铁锂材料。
其中,步骤(1)中:磷源为磷酸;锂源为氢氧化锂;锰源为硫酸锰、碳酸锰、乙酸锰和草酸锰中的一种或几种;铁源为硫酸亚铁、氯化亚铁、硝酸亚铁和草酸亚铁中的一种或几种;抗氧化剂为抗坏血酸;去离子水/PEG溶液中去离子水与PEG的体积比为5:1、2:1或1:1。
步骤(4)中保护气氛为95vol%Ar+5vol%H
2。
优先地,步骤(1)中所述去离子水/PEG溶液中去离子水与PEG的体积比 为2:1更佳。
优先地,步骤(1)中Ti
3C
2 MXene的加入量为该材料在最终产物中的含量为15wt%更佳。
优先地,步骤(2)中保温温度为180℃、保温时间为10小时更佳。
优先地,步骤(3)中所述烘干温度为60℃更佳。
优先地,步骤(4)中所述退火温度为650℃、退火时间为10h更佳。
本发明通过对磷酸锰铁锂进行Ti
3C
2 MXene包覆,有效地增强了磷酸铁锂的离子和电子传输能力以及结构稳定性,使该材料具备突出的电化学性能,所得的Ti
3C
2 MXene包覆磷酸锰铁锂材料在0.1C的首次放电容量为157.4mAh g
–1,首次库伦效率高于99%,1C的放电容量达到145.0mAh g
–1。
下面以具体实施例进一步说明本发明:
实施例1
将磷酸和氢氧化锂加入去体积比为2:1的离子水/PEG溶液中形成悬浮液A,随后将硫酸锰、硫酸亚铁、抗坏血酸和Ti
3C
2 MXene加入去离子水中形成悬浮液B,在持续搅拌条件下将悬浮液B滴加到悬浮液A中形成混合液,其中锂源、锰源、铁源和磷源的元素摩尔比Li:Mn:Fe:P=3:0.8:0.2:2;将得到的上述混合液转移到水热反应釜中,拧紧反应釜并将其置于烘箱中于180℃保温10h,反应完成后离心分离出水热产物并将其进行洗涤后在真空条件下于60℃烘干;最后将干燥的水热产物在95vol%Ar+5vol%H
2气氛下于650℃退火10h,退火完成后即可得黑色粉末的Ti
3C
2 MXene包覆磷酸锰铁锂材料;该产物中Ti
3C
2 MXene的含量为15wt%,其首次放电容量为157.4mAh g
–1,首次库伦效率99.6%。
实施例2
将磷酸和氢氧化锂加入去体积比为2:1的离子水/PEG溶液中形成悬浮液A,随后将碳酸锰、氯化亚铁、抗坏血酸和Ti
3C
2 MXene加入去离子水中形成悬浮液B,在持续搅拌条件下将悬浮液B滴加到悬浮液A中形成混合液,其中锂源、锰源、铁源和磷源的元素摩尔比Li:Mn:Fe:P=3:0.5:0.5:2;将得到的上述混合液转移到水热反应釜中,拧紧反应釜并将其置于烘箱中于140℃保温20h,反应完成后离心分离出水热产物并将其进行洗涤后在真空条件下于80℃烘干;最后将干燥的水热产物在95vol%Ar+5vol%H
2气氛下于500℃退火20h,退火完成 后即可得黑色粉末Ti
3C
2 MXene包覆磷酸锰铁锂材料;该产物中Ti
3C
2 MXene的含量为5wt%,其首次放电容量为130.4mAh g
–1,首次库伦效率95.6%。
实施例3
将磷酸和氢氧化锂加入去体积比为1:1的离子水/PEG溶液中形成悬浮液A,随后将乙酸锰、硝酸亚铁、抗坏血酸和Ti
3C
2 MXene加入去离子水中形成悬浮液B,在持续搅拌条件下将悬浮液B滴加到悬浮液A中形成混合液,其中锂源、锰源、铁源和磷源的元素摩尔比Li:Mn:Fe:P=3:0.7:0.3:2;将得到的上述混合液转移到水热反应釜中,拧紧反应釜并将其置于烘箱中于160℃保温15h,反应完成后离心分离出水热产物并将其进行洗涤后在真空条件下于30℃烘干;最后将干燥的水热产物在95vol%Ar+5vol%H
2气氛下于800℃退火5h,退火完成后即可得黑色粉末Ti
3C
2 MXene包覆磷酸锰铁锂材料;该产物中Ti
3C
2 MXene的含量为15wt%,其首次放电容量为135.1mAh g
–1,首次库伦效率96.5%。
实施例4
将磷酸和氢氧化锂加入去体积比为1:1的离子水/PEG溶液中形成悬浮液A,随后将乙酸锰和草酸锰、硫酸亚铁和草酸亚铁、抗坏血酸和Ti
3C
2 MXene加入去离子水中形成悬浮液B,在持续搅拌条件下将悬浮液B滴加到悬浮液A中形成混合液,其中锂源、锰源、铁源和磷源的元素摩尔比Li:Mn:Fe:P=3:0.6:0.4:2;将得到的上述混合液转移到水热反应釜中,拧紧反应釜并将其置于烘箱中于180℃保温10h,反应完成后离心分离出水热产物并将其进行洗涤后在真空条件下于50℃烘干;最后将干燥的水热产物在95vol%Ar+5vol%H
2气氛下于500℃退火20h,退火完成后即可得黑色粉末Ti
3C
2 MXene包覆磷酸锰铁锂材料;该产物中Ti
3C
2 MXene的含量为20wt%,其首次放电容量为150.3mAh g
–1,首次库伦效率97.1%。
实施例5
将磷酸和氢氧化锂加入去体积比为5:1的去离子水/PEG溶液中形成悬浮液A,随后将硫酸锰和乙酸锰、硫酸亚铁和硝酸亚铁、抗坏血酸和Ti
3C
2 MXene加入去离子水中形成悬浮液B,在持续搅拌条件下将悬浮液B滴加到悬浮液A中形成混合液,其中锂源、锰源、铁源和磷源的元素摩尔比Li:Mn:Fe:P=3:0.8:0.2:2;将得到的上述混合液转移到水热反应釜中,拧紧反应釜并将其置于烘箱中于200℃保温5h,反应完成后离心分离出水热产物并将其进行洗涤后 在真空条件下于70℃烘干;最后将干燥的水热产物在95vol%Ar+5vol%H
2气氛下于650℃退火10h,退火完成后即可得黑色粉末Ti
3C
2 MXene包覆磷酸锰铁锂材料;该产物中Ti
3C
2 MXene的含量为30wt%,其首次放电容量为140.6mAh g
–1,首次库伦效率96.6%。
本发明还采用未包覆的磷酸锰铁锂材料,即通过与在制备过程中不加入Ti
3C
2 MXene的未包覆磷酸锰铁锂材料作为对比,见图1、图2、图3,通过这些图不难发现,Ti
3C
2 MXene表面包覆能有效地增强磷酸锰铁锂材料的电化学性能,可得到一种具有高能量和功率密度的锂离子电池正极材料。
本领域的技术人员容易理解,以上所述仅为本发明的较佳实施例而已,并不用以限制本发明,凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等,均应包含在本发明的保护范围之内。
Claims (9)
- 一种锂离子电池正极材料,其特征在于:所述正极材料为Ti 3C 2MXene包覆磷酸锰铁锂材料,具体是将Ti 3C 2MXene均匀地包覆在磷酸锰铁锂纳米颗粒表面并形成导电网络。
- 如权利要求1所述的锂离子电池正极材料的制备方法,是将磷源和锂源加入去离子水/PEG溶液中形成悬浮液A,锰源、铁源、抗氧化剂和Ti 3C 2MXene加入去离子水中形成悬浮液B,在持续搅拌条件下将悬浮液B滴加到悬浮液A中形成混合液,再将此混合液转移到水热反应釜中于一定温度下保温一段时间,反应完成后离心分离出产物并将其洗涤烘干,最后将干燥的产物在气氛炉中进行烧结得到Ti 3C 2MXene包覆的磷酸锰铁锂材料。
- 权利要求2所述的锂离子电池正极材料的制备方法,包括以下具体步骤:(1)将磷源和锂源加入去离子水/PEG溶液中形成悬浮液A;将锰源、铁源、抗氧化剂和Ti 3C 2MXene加入去离子水中形成悬浮液B;在持续搅拌条件下将悬浮液B滴加到悬浮液A中形成混合液;其中锂源、锰源、铁源和磷源的元素摩尔比Li:Mn:Fe:P=3:1-x:x:2,0.1≤x≤0.5,Ti 3C 2MXene的加入量应使其在最终产物中的含量为5-30wt%;(2)将步骤(1)得到的混合液转移到水热反应釜中,拧紧反应釜后将其置于烘箱中于140-200℃的温度条件下保温5-20h;(3)反应完成后离心分离出水热产物并将其进行洗涤后在真空条件下温度烘干,烘干温度为30-80℃;(4)将步骤(3)所得干燥的水热产物在保护气氛下于500-800℃的温度条件下退火5-20h,即可得到Ti 3C 2MXene包覆磷酸锰铁锂材料。
- 权利要求3所述的锂离子电池正极材料的制备方法,其特征在于:所述磷源为磷酸。
- 权利要求3所述的锂离子电池正极材料的制备方法,其特征在于:所述锂源为氢氧化锂。
- 权利要求3所述的锂离子电池正极材料的制备方法,其特征在于:所述锰源为硫酸锰、碳酸锰、乙酸锰和草酸锰中的一种或几种。
- 权利要求3所述的锂离子电池正极材料的制备方法,其特征在于:所述铁源为硫酸亚铁、氯化亚铁、硝酸亚铁和草酸亚铁中的一种或几种。
- 权利要求3所述的锂离子电池正极材料的制备方法,其特征在于:所述抗氧化剂为抗坏血酸。
- 权利要求3所述的锂离子电池正极材料的制备方法,其特征在于:所述去离子水/PEG溶液中去离子水与PEG的体积比为5:1、2:1或1:1。
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