CN114023953A - Modified lithium iron manganese phosphate cathode material and preparation method and application thereof - Google Patents
Modified lithium iron manganese phosphate cathode material and preparation method and application thereof Download PDFInfo
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- CN114023953A CN114023953A CN202111292626.0A CN202111292626A CN114023953A CN 114023953 A CN114023953 A CN 114023953A CN 202111292626 A CN202111292626 A CN 202111292626A CN 114023953 A CN114023953 A CN 114023953A
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- lithium iron
- manganese phosphate
- iron manganese
- phosphate
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- DVATZODUVBMYHN-UHFFFAOYSA-K lithium;iron(2+);manganese(2+);phosphate Chemical class [Li+].[Mn+2].[Fe+2].[O-]P([O-])([O-])=O DVATZODUVBMYHN-UHFFFAOYSA-K 0.000 title claims abstract description 98
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000010406 cathode material Substances 0.000 title claims description 19
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims abstract description 60
- 239000000463 material Substances 0.000 claims abstract description 46
- 229960003638 dopamine Drugs 0.000 claims abstract description 30
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 27
- 239000000872 buffer Substances 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 239000007774 positive electrode material Substances 0.000 claims abstract description 12
- 238000001354 calcination Methods 0.000 claims abstract description 11
- 239000002244 precipitate Substances 0.000 claims abstract description 11
- 239000002904 solvent Substances 0.000 claims abstract description 11
- 239000008055 phosphate buffer solution Substances 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims description 14
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 13
- 229910001416 lithium ion Inorganic materials 0.000 claims description 13
- 229910014616 LiMnFePO4 Inorganic materials 0.000 claims description 10
- 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 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- 239000011247 coating layer Substances 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 7
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical group [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 claims description 6
- 239000003125 aqueous solvent Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 239000007983 Tris buffer Substances 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 239000011572 manganese Substances 0.000 claims description 5
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 claims description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- 239000003963 antioxidant agent Substances 0.000 claims description 4
- 230000003078 antioxidant effect Effects 0.000 claims description 4
- 235000006708 antioxidants Nutrition 0.000 claims description 4
- 229960005070 ascorbic acid Drugs 0.000 claims description 4
- 235000010323 ascorbic acid Nutrition 0.000 claims description 4
- 239000011668 ascorbic acid Substances 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 4
- PQVSTLUFSYVLTO-UHFFFAOYSA-N ethyl n-ethoxycarbonylcarbamate Chemical compound CCOC(=O)NC(=O)OCC PQVSTLUFSYVLTO-UHFFFAOYSA-N 0.000 claims description 4
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 claims description 4
- 229910052744 lithium Inorganic materials 0.000 claims description 4
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium hydroxide monohydrate Substances [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 claims description 4
- 229940040692 lithium hydroxide monohydrate Drugs 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- ISPYRSDWRDQNSW-UHFFFAOYSA-L manganese(II) sulfate monohydrate Chemical compound O.[Mn+2].[O-]S([O-])(=O)=O ISPYRSDWRDQNSW-UHFFFAOYSA-L 0.000 claims description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims description 4
- 239000011574 phosphorus Substances 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 2
- 239000010405 anode material Substances 0.000 abstract description 7
- 239000003575 carbonaceous material Substances 0.000 abstract description 6
- 108091006149 Electron carriers Proteins 0.000 abstract description 5
- 150000002500 ions Chemical class 0.000 abstract description 5
- 238000000576 coating method Methods 0.000 description 19
- 239000011248 coating agent Substances 0.000 description 17
- 239000007853 buffer solution Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 239000002131 composite material Substances 0.000 description 7
- 239000003792 electrolyte Substances 0.000 description 6
- 230000009286 beneficial effect Effects 0.000 description 5
- 238000007599 discharging Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 230000014759 maintenance of location Effects 0.000 description 5
- 229920001690 polydopamine Polymers 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000003763 carbonization Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 230000003993 interaction Effects 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
- FYFFGSSZFBZTAH-UHFFFAOYSA-N methylaminomethanetriol Chemical compound CNC(O)(O)O FYFFGSSZFBZTAH-UHFFFAOYSA-N 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- 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 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229910020489 SiO3 Inorganic materials 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000003851 biochemical process Effects 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 238000010835 comparative analysis Methods 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
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- 239000011888 foil Substances 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 238000007709 nanocrystallization Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
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Images
Classifications
-
- 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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
-
- 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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention provides a modified lithium iron manganese phosphate positive electrode material and a preparation method and application thereof, wherein the preparation method comprises the following steps: (1) mixing a lithium manganese iron phosphate material with an alkaline buffer solvent to obtain a lithium manganese iron phosphate buffer solution; (2) mixing the lithium manganese iron phosphate buffer solution obtained in the step (1) with dopamine, centrifuging to obtain a precipitate, calcining the obtained precipitate to obtain the modified lithium manganese iron phosphate anode material, wherein compared with a conventional carbon-coated material, the nitrogen-doped carbon material can provide more electron carriers in a conductive region, so that LiMnFePO is effectively enhanced4Electron conductivity and ion diffusivity of the material.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and relates to a modified lithium iron manganese phosphate positive electrode material, and a preparation method and application thereof.
Background
Lithium ion batteries, one of the new energy sources, have been widely used in electronic products, electric vehicles, and implantable medical devices due to their advantages, such as high energy density and long service life. With the expansion of the application range of the lithium ion battery, higher requirements are put forward on the safety of battery materials, the high-rate charge and discharge performance of the battery and the cycle life.
As a isomorphous substance of lithium iron phosphate, the lithium iron manganese phosphate material is a novel anode material of a lithium ion battery, has the same crystal structure as lithium iron phosphate, and has the characteristics of safety, long service life and low cost, but the lithium iron manganese phosphate material has poor conductivity, so a great deal of research is devoted to improving the electrochemical characteristics at present, and the method comprises the steps of particle size nanocrystallization, cation doping, carbon coating on the surface and the like; LiMnFePO4The combination with a highly conductive carbonaceous material is believed to enhance LiMnFePO4One of the most common and effective methods for capacity and rate capability, surface conductive coatings (e.g., carbon coatings) are used to augment limnffepo4Conductivity of (2), prevention of LiMnFePO4Directly contacting with the electrolyte, thereby improving the high rate capacity and the cycling stability. However, the current adopted conductive carbon coating has the conditions of difficult control of the thickness of the carbon layer, uneven coating of the carbon layer, general conductive effect and the like, and in addition, the LiMnFePO is reduced due to the high carbon content4Energy density and power density of the material.
CN107046128A discloses a preparation method of a lithium iron manganese phosphate composite material, wherein the lithium iron manganese phosphate composite material comprises lithium iron manganese phosphate and a hydrophobic material coated on the surface of the lithium iron manganese phosphate. Because the hydrophobic material is coated on the surface of the lithium manganese iron phosphate, the coated material is insoluble in water and resistant to electrolyte; therefore, compared with the traditional lithium iron manganese phosphate material, the lithium iron manganese phosphate composite material can solve the problem that the lithium iron manganese phosphate battery is easy to absorb water, but the conductivity of the lithium iron manganese phosphate composite material is not obviously improved.
CN111710846A discloses an anion-doped lithium manganese iron phosphate material, Li1+x(Mn1-y-zFeyMz)a(PO4)(SiO3)bThe method comprises the steps of obtaining a silicon-containing lithium manganese iron phosphate precursor through a one-step method, and then sintering to obtain a high-compaction product, wherein the lithium manganese iron phosphate material has poor ionic conductivity due to the existence of silicon.
The scheme has the problem that the prepared lithium iron manganese phosphate material has poor conductivity or poor ionic conductivity, so that the development of the lithium iron manganese phosphate material with good conductivity and good ionic conductivity is necessary.
Disclosure of Invention
The invention aims to provide a modified lithium manganese iron phosphate positive electrode material and a preparation method and application thereof, wherein dopamine can be subjected to high-temperature carbonization treatment to obtain a nitrogen-doped carbon film, compared with the conventional carbon-coated material, the nitrogen-doped carbon material can provide more electron carriers in a conductive region, and the electrochemical performance of the lithium manganese iron phosphate material is improved through good electronic conductivity, so that the electronic conductivity and the ion diffusivity of the lithium manganese iron phosphate material are effectively enhanced; the introduction of nitrogen-containing functional groups enhances the wettability and affinity of carbon to electrolyte, and is beneficial to LiMnFePO4Dispersing; the nitrogen doped carbon coating may additionally provide an external defect that serves as an additional lithium ion storage site.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a preparation method of a modified lithium iron manganese phosphate positive electrode material, which comprises the following steps:
(1) mixing a lithium manganese iron phosphate material with an alkaline buffer solvent to obtain a lithium manganese iron phosphate buffer solution;
(2) and (2) mixing the lithium iron manganese phosphate buffer solution obtained in the step (1) with dopamine, carrying out centrifugal treatment to obtain a precipitate, and calcining the obtained precipitate to obtain the modified lithium iron manganese phosphate cathode material.
The method uses the alkaline buffer solution as a medium to mix dopamine and lithium manganese iron phosphate, the dopamine is a compound of catechol and amine functional groups, the dopamine is self-polymerized under alkaline conditions, a polydopamine coating can be formed on almost any surface, the thickness of the coating is uniform and can be adjusted, the good coating effect on the lithium manganese iron phosphate material can be realized, the dopamine can be subjected to high-temperature carbonization treatment to obtain a nitrogen-doped carbon film, and the lithium manganese iron phosphate material is coated by the dopamine to obtain the carbon-nitrogen co-doped lithium manganese iron phosphate composite material.
Compared with the conventional carbon-coated material, the nitrogen-doped carbon material can provide more electron carriers in the conductive region, and the electrochemical performance of the lithium manganese iron phosphate material is improved through good electron conductivity, so that the electron conductivity and the ion diffusivity of the lithium manganese iron phosphate material are effectively enhanced; the introduction of nitrogen-containing functional groups enhances the wettability and affinity of carbon to electrolyte, and is beneficial to LiMnFePO4Dispersing; the nitrogen doped carbon coating may additionally provide an external defect that serves as an additional lithium ion storage site.
Preferably, the lithium manganese iron phosphate positive electrode material in the step (1) is prepared by the following method: adding a lithium source, an iron source, a manganese source, a phosphorus source and an antioxidant into an aqueous solvent under a stirring state, fully stirring and uniformly mixing, transferring to a high-temperature condition for hydro-thermal synthesis, and filtering and separating the solution to obtain the lithium iron manganese phosphate powder material.
Preferably, the lithium source comprises lithium hydroxide monohydrate;
preferably, the iron source comprises ferrous sulfate heptahydrate;
preferably, the manganese source comprises manganese sulfate monohydrate;
preferably, the phosphorus source comprises phosphoric acid;
preferably, the antioxidant is ascorbic acid;
preferably, the aqueous solvent is an aqueous solution, or an aqueous solution containing an ionic or organic solvent;
preferably, the elevated temperature is 150-.
Preferably, the alkaline buffer solvent of step (1) comprises tris buffer.
Preferably, the pH of the alkaline buffer solvent is 7.5-9, such as: 7.5, 7.8, 8, 8.2, 8.5 or 9, etc.
Preferably, in the lithium iron manganese phosphate buffer solution in the step (1), the concentration of the lithium iron manganese phosphate is 20
About 50mg/mL, for example: 20mg/mL, 25mg/mL, 30mg/mL, 35mg/mL, 40mg/mL, 50mg/mL, or the like.
Preferably, the mass ratio of the dopamine to the lithium iron manganese phosphate material in the step (2) is 5: 95-25: 75, preferably 1: 9-1: 4, for example: 5:95, 10:90, 15:85, 20:80 or 25:75, preferably 10: 90-20: 80.
Preferably, the temperature of the calcination treatment in the step (2) is 600-800 ℃, for example: 600 deg.C, 620 deg.C, 650 deg.C, 700 deg.C, 750 deg.C or 800 deg.C, etc.
Preferably, the time of the calcination treatment is 4-8 h, such as: 4h, 4.5h, 5h, 6h, 7h or 8h and the like.
Preferably, the calcination treatment is carried out under an inert atmosphere.
In a second aspect, the invention provides a modified lithium iron manganese phosphate positive electrode material, which is prepared by the method in the first aspect, and comprises a core and a coating layer, wherein the core is LiMnFePO4And the coating layer is a carbon-nitrogen co-doped carbon coating layer.
According to the modified lithium iron manganese phosphate anode material, the carbon-nitrogen co-doped coating layer is coated on the outer layer of the modified lithium iron manganese phosphate anode material, on one hand, the carbon material doped with heteroatoms (particularly nitrogen atoms) has higher conductivity, and can provide more electron carriers in a conductive region, so that the electron conductivity and lithium ion diffusion are effectively enhanced, and on the other hand, the introduction of nitrogen-containing functional groups increases carbon and LiMnFePO4The interaction between the carbon and the electrolyte improves the wettability and the affinity of the carbon and is beneficial to LiMnFePO4Dispersing; in addition, the nitrogen-doped carbon coating can also provide external defects as an additional lithium ion storage position, and the modified lithium iron manganese phosphate cathode material provided by the invention is used as a cathodeThe material can obtain the lithium ion battery positive pole piece with higher conductivity, capacity retention rate and cycle performance.
In a third aspect, the invention provides a positive electrode plate, which comprises the modified lithium iron manganese phosphate positive electrode material according to the second aspect.
In a fourth aspect, the invention provides a lithium ion battery, which comprises the positive electrode plate according to the third aspect.
Compared with the prior art, the invention has the following beneficial effects:
(1) the method uses the alkaline buffer solution as a medium to mix dopamine and lithium manganese iron phosphate, the dopamine is a compound of catechol and amine functional groups, the dopamine is self-polymerized under alkaline conditions, a polydopamine coating can be formed on almost any surface, the thickness of the coating is uniform and can be adjusted, the good coating effect on the lithium manganese iron phosphate material can be realized, the dopamine can be subjected to high-temperature carbonization treatment to obtain a nitrogen-doped carbon film, and the lithium manganese iron phosphate material is coated by the dopamine to obtain the carbon-nitrogen co-doped lithium manganese iron phosphate composite material.
(2) The modified lithium iron manganese phosphate cathode material has better conductivity, increases reaction sites, and reduces the energy barrier of ion permeation.
(3) The gram capacity of a battery prepared by using the modified anode material can reach more than 150.16mAh/g, and the capacity retention rate after 50 cycles can reach more than 96.99%.
Drawings
Fig. 1 is an SEM image of the modified lithium iron manganese phosphate positive electrode material of example 1.
Fig. 2 is an SEM magnified view of the modified lithium iron manganese phosphate positive electrode material of example 1.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
The embodiment provides a modified lithium iron manganese phosphate cathode material, and a preparation method of the modified lithium iron manganese phosphate cathode material comprises the following steps:
(1) lithium hydroxide monohydrate, ferrous sulfate heptahydrate, manganese sulfate monohydrate, phosphoric acid and ascorbic acid are adopted as raw materials, the raw materials are respectively added into an aqueous solvent under the stirring state, the mixture is fully stirred and uniformly mixed, then the mixture is transferred to a high-temperature condition for hydro-thermal synthesis, and then the solution is filtered and separated, so that the lithium iron manganese phosphate powder material is obtained. (ii) a
(2) Mixing a lithium iron manganese phosphate material with a trihydroxymethyl aminomethane buffer solution with the pH value of 8 to obtain a buffer solution with the concentration of the lithium iron manganese phosphate of 30 mg/mL;
(3) mixing the lithium iron manganese phosphate buffer solution obtained in the step (1) with dopamine, wherein the mass ratio of the dopamine to the lithium iron manganese phosphate material is 10:90, carrying out centrifugal treatment to obtain a precipitate, and calcining the obtained precipitate at 700 ℃ for 6 hours in an inert atmosphere to obtain the modified lithium iron manganese phosphate anode material, wherein an SEM image of the modified lithium iron manganese phosphate anode material is shown in a figure 1-2.
Example 2
The embodiment provides a modified lithium iron manganese phosphate cathode material, and a preparation method of the modified lithium iron manganese phosphate cathode material comprises the following steps:
(1) lithium hydroxide monohydrate, ferrous sulfate heptahydrate, manganese sulfate monohydrate, phosphoric acid and ascorbic acid are adopted as raw materials, the raw materials are respectively added into an aqueous solvent under the stirring state, the mixture is fully stirred and uniformly mixed, then the mixture is transferred to a high-temperature condition for hydro-thermal synthesis, and then the solution is filtered and separated, so that the lithium iron manganese phosphate powder material can be obtained;
(2) mixing a lithium iron manganese phosphate material with a trihydroxymethyl aminomethane buffer solution with the pH value of 8.5 to obtain a buffer solution with the concentration of the lithium iron manganese phosphate of 40 mg/mL;
(3) and (2) mixing the lithium manganese iron phosphate buffer solution obtained in the step (1) with dopamine, wherein the mass ratio of the dopamine to the lithium manganese iron phosphate material is 15:85, carrying out centrifugal treatment to obtain a precipitate, and calcining the obtained precipitate at 750 ℃ for 5 hours in an inert atmosphere to obtain the modified lithium manganese iron phosphate cathode material.
Example 3
This example is different from example 1 only in that the tris buffer solution in step (2) has a pH of 7.2, and the other conditions and parameters are exactly the same as those in example 1.
Example 4
This example is different from example 1 only in that the tris buffer solution in step (2) has a pH of 9.5, and the other conditions and parameters are exactly the same as those in example 1.
Example 5
The difference between the present embodiment and embodiment 1 is only that the mass ratio of the dopamine and the lithium iron manganese phosphate material in step (2) is 8:92, and the other conditions and parameters are completely the same as those in embodiment 1.
Example 6
The difference between the present embodiment and embodiment 1 is only that the mass ratio of the dopamine and the lithium iron manganese phosphate material in step (2) is 23:77, and the other conditions and parameters are completely the same as those in embodiment 1.
Comparative example 1
This comparative example is different from example 1 only in that tris buffer was replaced with ethanol, and the other conditions and parameters were exactly the same as those of example 1.
Comparative example 2
This comparative example differs from example 1 only in that dopamine was replaced by glucose, and the other conditions and parameters were exactly the same as in example 1.
And (3) performance testing:
the modified lithium iron manganese phosphate positive electrode material prepared in the embodiment and the comparative example is uniformly stirred with a conductive agent, a binder and an organic solvent, then is coated on an aluminum foil, and is rolled to obtain a modified lithium iron manganese phosphate positive electrode sheet; and (4) assembling the positive plate into the button cell and then carrying out performance test. The gram capacity test method is as follows: charging the battery to 4.3V at constant current and constant voltage by adopting 0.1C, stopping the current to be 0.02C, then discharging to 2.5V by adopting 0.1C, and calculating the gram discharge capacity of the battery; and (3) cycle testing: charging the battery to 4.3V at a constant current and a constant voltage of 1C, stopping the current to 0.02C, then discharging to 2.5V at a constant current of 1C, circulating for 50 circles, and then carrying out comparative analysis on the capacity retention rate of the battery; the multiplying power test method comprises the following steps: and respectively adopting 0.1/0.2/0.33/0.5/1C to charge the battery to 4.3V at constant current and constant voltage, and the cut-off current is 0.02C, then respectively applying 0.1/0.2/0.33/0.5/1C to discharge the battery to 2.5V, and calculating the multiplying power discharge gram capacity of the battery. The test results are shown in tables 1-2 below:
TABLE 1
| 0.1C gram capacity (mAh/g) | Capacity retention (%) | |
| Example 1 | 164.3 | 100.72 |
| Example 2 | 165.5 | 100.84 |
| Example 3 | 162.9 | 100.40 |
| Example 4 | 163.3 | 100.46 |
| Example 5 | 162.6 | 97.02 |
| Example 6 | 161.8 | 97.15 |
| Comparative example 1 | 147.7 | 66.99 |
| Comparative example 2 | 159.0 | 89.83 |
TABLE 2
As can be seen from table 1, in examples 1 to 6, the gram capacity of the battery prepared by using the modified cathode material of the present invention can reach 161.8mAh/g or more, the capacity retention rate after 50 cycles can reach 96.99% or more, and the battery has good rate capability, the 0.2C discharge gram capacity can reach 156.6mAh/g or more, the 0.33C gram capacity can reach 153.4mAh/g or more, the 0.5C gram capacity can reach 151.1mAh/g or more, and the 1C gram capacity can reach 146mAh/g or more. Meanwhile, the change of the gram-discharging capacity of the battery under different multiplying powers is small, and the irreversible attenuation of the gram-discharging capacity caused by charging and discharging of a user under different systems can be avoided, so that the service life of the battery is greatly prolonged.
Compared with the examples 3-4, the performance of the prepared modified lithium iron manganese phosphate cathode material is influenced by the pH of the buffer solvent, the performance of the prepared modified lithium iron manganese phosphate cathode material is excellent by controlling the pH of the buffer solvent to be 7.5-9, if the pH of the buffer solvent is too low, dopamine cannot be polymerized, a polydopamine coating cannot be formed, the coating effect is influenced, if the pH of the buffer solvent is too high, the polydopamine polymerization coating is damaged by too strong alkalinity, the coating effect is influenced, and the performance of the prepared modified lithium iron manganese phosphate cathode material is reduced.
Compared with the examples 5-6, the quality ratio of the dopamine to the lithium iron manganese phosphate material can affect the performance of the prepared modified lithium iron manganese phosphate cathode material, the quality ratio of the dopamine to the lithium iron manganese phosphate material is controlled to be 10: 90-20: 80, the prepared modified lithium iron manganese phosphate cathode material has good electrochemical performance, if the addition amount of the dopamine is too low, the active material cannot be coated, the conductivity of the material is reduced, and if the addition amount of the dopamine is too high, the formed coating layer is too thick, and LiMnFePO is affected4Energy density and power density of the material.
Compared with the comparative example 1, the method has the advantages that the buffer solution is used as a medium, so that dopamine can be automatically polymerized into poly-dopamine under an alkaline condition, and a compact and uniform carbon layer can be coated on the surface of the lithium iron manganese phosphate material; the buffer solution has high solubility in aqueous solution, is generally used for stabilizing the pH value of a reaction system, and has stronger buffer capacity between the pH value of 7.5 and 9.0; in addition, the buffer solution has small interference in the biochemical process, does not precipitate with calcium ions, magnesium ions and heavy metal ions, and ensures the purity of a reaction system and reaction products.
Compared with the comparative example 2, the embodiment 1 has the advantages that dopamine is adopted to coat the lithium manganese iron phosphate material, so that the carbon-nitrogen co-doped lithium manganese iron phosphate composite material can be obtained; on one hand, the carbon material doped with the heteroatom (particularly nitrogen atom) not only has higher conductivity and can provide more electron carriers in a conductive region, thereby effectively enhancing the electron conductivity and lithium ion diffusion, but also adds carbon and LiMnFePO by introducing a nitrogen-containing functional group4The interaction between the carbon and the electrolyte improves the wettability and the affinity of the carbon and is beneficial to LiMnFePO4Dispersing; in addition to this, the nitrogen-doped carbon coating may also provide external defects as an extra layerThe lithium ion storage location of (a).
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.
Claims (10)
1. The preparation method of the modified lithium iron manganese phosphate cathode material is characterized by comprising the following steps of:
(1) mixing a lithium manganese iron phosphate material with an alkaline buffer solvent to obtain a lithium manganese iron phosphate buffer solution;
(2) and (2) mixing the lithium iron manganese phosphate buffer solution obtained in the step (1) with dopamine, carrying out centrifugal treatment to obtain a precipitate, and calcining the obtained precipitate to obtain the modified lithium iron manganese phosphate cathode material.
2. The preparation method of claim 1, wherein the lithium iron manganese phosphate positive electrode material in the step (1) is prepared by a method comprising the following steps: adding a lithium source, an iron source, a manganese source, a phosphorus source and an antioxidant into an aqueous solvent under a stirring state, fully stirring and uniformly mixing, transferring to a high-temperature condition for hydro-thermal synthesis, and filtering and separating the solution to obtain the lithium iron manganese phosphate powder material.
3. The method of claim 2, wherein the lithium source comprises lithium hydroxide monohydrate;
preferably, the iron source comprises ferrous sulfate heptahydrate;
preferably, the manganese source comprises manganese sulfate monohydrate;
preferably, the phosphorus source comprises phosphoric acid;
preferably, the antioxidant is ascorbic acid;
preferably, the aqueous solvent is an aqueous solution, or an aqueous solution containing an ionic or organic solvent;
preferably, the elevated temperature is 150-.
4. The method according to any one of claims 1 to 3, wherein the basic buffer solvent of step (1) comprises a tris buffer;
preferably, the pH value of the alkaline buffer solvent is 7.5-9.
5. The preparation method according to any one of claims 1 to 4, wherein the concentration of the lithium iron manganese phosphate in the lithium iron manganese phosphate buffer solution in the step (1) is 20 to 50 mg/mL.
6. The preparation method according to any one of claims 1 to 5, wherein the mass ratio of the dopamine to the lithium iron manganese phosphate material in the step (2) is 5: 95-25: 75, preferably 10: 90-20: 80.
7. The method according to any one of claims 1 to 6, wherein the temperature of the calcination treatment in the step (2) is 600 to 800 ℃;
preferably, the calcining treatment time is 4-8 h;
preferably, the calcination treatment is carried out under an inert atmosphere.
8. The modified lithium iron manganese phosphate cathode material is characterized by being prepared by the method of any one of claims 1 to 7, and comprising a core and a coating layer, wherein the core is LiMnFePO4And the coating layer is a carbon-nitrogen co-doped carbon coating layer.
9. A positive electrode plate, characterized by comprising the modified lithium iron manganese phosphate positive electrode material according to claim 8.
10. A lithium ion battery comprising the positive electrode sheet of claim 9.
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