CN114243006A - Lithium iron manganese phosphate positive electrode material, preparation method thereof and soft package lithium battery - Google Patents
Lithium iron manganese phosphate positive electrode material, preparation method thereof and soft package lithium battery Download PDFInfo
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- CN114243006A CN114243006A CN202111565225.8A CN202111565225A CN114243006A CN 114243006 A CN114243006 A CN 114243006A CN 202111565225 A CN202111565225 A CN 202111565225A CN 114243006 A CN114243006 A CN 114243006A
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- Prior art keywords
- lithium iron
- manganese phosphate
- limn
- iron manganese
- carbon
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- 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 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title claims description 17
- 239000007774 positive electrode material Substances 0.000 title claims description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title abstract description 20
- 229910052744 lithium Inorganic materials 0.000 title abstract description 20
- 239000000463 material Substances 0.000 claims abstract description 111
- 238000001035 drying Methods 0.000 claims abstract description 37
- 239000003125 aqueous solvent Substances 0.000 claims abstract description 31
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 29
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 28
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 25
- 238000002156 mixing Methods 0.000 claims abstract description 18
- 238000001914 filtration Methods 0.000 claims abstract description 8
- 239000011572 manganese Substances 0.000 claims abstract description 8
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 6
- 229910052751 metal Inorganic materials 0.000 claims abstract description 6
- 239000002184 metal Substances 0.000 claims abstract description 6
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 6
- 229910052706 scandium Inorganic materials 0.000 claims abstract description 6
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- 239000000203 mixture Substances 0.000 claims description 17
- 229910001416 lithium ion Inorganic materials 0.000 claims description 13
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 12
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 11
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 229910019500 Mg0.05PO4 Inorganic materials 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 8
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 150000001298 alcohols Chemical class 0.000 claims description 3
- 150000001408 amides Chemical class 0.000 claims description 3
- 150000002576 ketones Chemical class 0.000 claims description 3
- 150000003462 sulfoxides Chemical class 0.000 claims description 3
- 229910015862 LiMn0.75Fe0.25PO4 Inorganic materials 0.000 claims description 2
- 229910015855 LiMn0.7Fe0.3PO4 Inorganic materials 0.000 claims description 2
- 229910015883 LiMn0.80Fe0.20PO4 Inorganic materials 0.000 claims description 2
- 229910015918 LiMn0.85Fe0.15PO4 Inorganic materials 0.000 claims description 2
- 239000012298 atmosphere Substances 0.000 description 26
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 21
- 238000003756 stirring Methods 0.000 description 20
- 238000001816 cooling Methods 0.000 description 18
- 239000007787 solid Substances 0.000 description 16
- 239000002245 particle Substances 0.000 description 15
- 238000011056 performance test Methods 0.000 description 15
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 14
- 239000006255 coating slurry Substances 0.000 description 14
- 239000000758 substrate Substances 0.000 description 14
- 229910015645 LiMn Inorganic materials 0.000 description 13
- RGVLTEMOWXGQOS-UHFFFAOYSA-L manganese(2+);oxalate Chemical compound [Mn+2].[O-]C(=O)C([O-])=O RGVLTEMOWXGQOS-UHFFFAOYSA-L 0.000 description 9
- 239000012299 nitrogen atmosphere Substances 0.000 description 9
- 239000002131 composite material Substances 0.000 description 8
- 239000002243 precursor Substances 0.000 description 8
- 239000001569 carbon dioxide Substances 0.000 description 7
- 229910002092 carbon dioxide Inorganic materials 0.000 description 7
- 235000006408 oxalic acid Nutrition 0.000 description 7
- 229910052782 aluminium Inorganic materials 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- FTXWZTQWJZKPTB-UHFFFAOYSA-H [Li+].P(=O)([O-])([O-])[O-].[Mn+2].[Li+].P(=O)([O-])([O-])[O-].[Fe+2] Chemical compound [Li+].P(=O)([O-])([O-])[O-].[Mn+2].[Li+].P(=O)([O-])([O-])[O-].[Fe+2] FTXWZTQWJZKPTB-UHFFFAOYSA-H 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 239000010406 cathode material Substances 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000011812 mixed powder Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 3
- 239000013543 active substance Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 238000005538 encapsulation Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- 238000004806 packaging method and process Methods 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- CEBNZLKRYBQXSF-UHFFFAOYSA-E [Li+].[Fe+2].P(=O)([O-])([O-])[O-].[Mn+2].[C+4].P(=O)([O-])([O-])[O-].P(=O)([O-])([O-])[O-] Chemical compound [Li+].[Fe+2].P(=O)([O-])([O-])[O-].[Mn+2].[C+4].P(=O)([O-])([O-])[O-].P(=O)([O-])([O-])[O-] CEBNZLKRYBQXSF-UHFFFAOYSA-E 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 235000006748 manganese carbonate Nutrition 0.000 description 2
- 239000011656 manganese carbonate Substances 0.000 description 2
- 229940093474 manganese carbonate Drugs 0.000 description 2
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 2
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 description 2
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000012785 packaging film Substances 0.000 description 2
- 229920006280 packaging film Polymers 0.000 description 2
- 238000011085 pressure filtration Methods 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 239000004277 Ferrous carbonate Substances 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
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 1
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 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 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- RAQDACVRFCEPDA-UHFFFAOYSA-L ferrous carbonate Chemical compound [Fe+2].[O-]C([O-])=O RAQDACVRFCEPDA-UHFFFAOYSA-L 0.000 description 1
- 235000019268 ferrous carbonate Nutrition 0.000 description 1
- 229960004652 ferrous carbonate Drugs 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 239000008236 heating water Substances 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 229910000015 iron(II) carbonate Inorganic materials 0.000 description 1
- 238000010902 jet-milling Methods 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- -1 lithium hexafluorophosphate Chemical compound 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- PGXWDLGWMQIXDT-UHFFFAOYSA-N methylsulfinylmethane;hydrate Chemical compound O.CS(C)=O PGXWDLGWMQIXDT-UHFFFAOYSA-N 0.000 description 1
- 235000019837 monoammonium phosphate Nutrition 0.000 description 1
- WHQSYGRFZMUQGQ-UHFFFAOYSA-N n,n-dimethylformamide;hydrate Chemical compound O.CN(C)C=O WHQSYGRFZMUQGQ-UHFFFAOYSA-N 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 238000006864 oxidative decomposition reaction Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- OVARTBFNCCXQKS-UHFFFAOYSA-N propan-2-one;hydrate Chemical compound O.CC(C)=O OVARTBFNCCXQKS-UHFFFAOYSA-N 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 230000000391 smoking effect Effects 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
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
- H01M4/58—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
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- 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)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Disclosed is a lithium iron manganese phosphate/carbon material having the general formula: li (Mn)1‑x‑yFexMy)PO4and/C, wherein: x is more than or equal to 0.1 and less than or equal to 0.45, and y is more than or equal to 0 and less than or equal to 0.1; the doping element M is a divalent metal and is selected from one or more of Mg, Co, Ca, Sc, Ni and Zn; according to weight, the manganese lithium iron phosphate accounts for 97-99 wt% of the whole material, and the carbon accounts for 1.0-3 wt%; it is prepared by the following method: (i) providing a lithium iron manganese phosphate/carbon material; (ii) mixing an aqueous solvent with the lithium iron manganese phosphate/carbon material for at least 10 minutes; (iii) filtering and drying. The soft package lithium battery prepared by the material has low expansion performance.
Description
Technical Field
The invention relates to a lithium iron manganese phosphate lithium ion battery anode material and a preparation method thereof. The soft package lithium ion battery prepared by the anode material has improved volume expansion performance.
Background
The lithium ion battery is a mainstream energy storage device of the current electric automobile, determines the characteristics of the electric automobile such as power performance, endurance mileage, service life, environmental tolerance, cost and the like, and is a key component of the electric automobile.
Compared with the conventional hard-shell batteries, namely cylindrical batteries and square batteries, the soft-pack lithium batteries are batteries which adopt an aluminum-plastic composite film as a shell (instead of adopting a metal material as the shell as in the case of the square and cylindrical batteries), although the internal compositions (positive electrode, negative electrode, diaphragm and electrolyte) of the soft-pack lithium batteries are not greatly different. The soft-package lithium battery has the advantages of small volume and light weight, and is more suitable for portable application with higher space or thickness requirements, such as 3C consumer electronics. At present, the single battery is also developing towards the direction of large capacity and high rate, which will more meet the requirements of the fields such as new energy automobiles and the like for the mobile power supply.
Generally, the advantages of soft-packed lithium batteries are:
good safety performance: the soft package lithium battery is structurally packaged by an aluminum plastic film, when thermal management is out of control or puncture occurs, the soft package can provide a buffer space for the battery cell, bulging deformation occurs, and finally ignition or smoking can occur, but explosion cannot occur;
-light weight: the soft package lithium battery is lighter than a steel shell lithium battery with the same capacity by about 40 percent and lighter than an aluminum shell battery by about 20 percent, so that the soft package lithium battery has higher energy density;
large capacity: the soft package lithium battery has 10-15% higher capacity than a steel shell battery with the same size and 5-10% higher capacity than an aluminum shell battery;
internal resistance is small: the internal resistance of the soft package battery is small, the internal resistance of the current domestic soft package lithium battery core can be smaller than 35m omega, and the self consumption of the battery is greatly reduced.
One disadvantage of soft-packed lithium batteries, however, is that volume expansion, i.e., bulging, can occur when severe. The reason why the bulge is considered to occur is:
thickness increase due to expansion of the battery pole piece during cycling;
-swelling due to oxidative decomposition of the electrolyte to gas evolution;
the bulging caused by the process defects of moisture, corner damage and the like due to the untight packaging of the battery.
To address the bulging problem of soft-packed lithium batteries, many solutions have been proposed in the art. For example:
CN208862033U discloses a soft packet of lithium cell structure, including electric core, be equipped with the diaphragm on the electric core, install positive pole and negative pole on the diaphragm, all be equipped with utmost point ear on positive pole and the negative pole, the last parcel of electric core has the plastic-aluminum packaging film, and the top of electric core installs the snuffle valve, be equipped with the piston on the snuffle valve, the spring is installed to the top of piston, the hole that loses heart has been seted up on the lateral wall of snuffle valve, the disappointing pipe is installed to the hole that loses heart, the last cover of electric core is equipped with the protective housing, through the snuffle valve that is equipped with, can lose heart when the certain degree is reachd to the swell, guarantees that the degree of its swell is in controllable range, can effectually prevent because the swell, leads to the plastic-aluminum packaging film to prop brokenly, causes the problem that electrolyte was revealed.
CN210668434U discloses soft packet of lithium cell packaging structure, including two-layer encapsulation membrane, be equipped with the chamber of acceping that is used for holding electric core between the two-layer encapsulation membrane, just the edge of two-layer encapsulation membrane overlaps and fuses into through the hot-pressing and be used for sealing the banding of acceping the chamber, wear to be equipped with one at least stylolite on the banding, be equipped with on the banding not quilt the sutural explosion-proof area of suture, explosion-proof area is close to one side of outward flange is extended and is formed the pressure relief portion, the pressure relief portion is inlayed and is had the quick-operation joint that has the explosion-proof valve.
Above-mentioned soft packet of lithium cell sets up the security that loses heart device increased the battery through the packaging structure. They do not mention how to prevent the soft pack lithium battery from bulging at the source.
Therefore, there is still a need in the art to provide a lithium iron manganese phosphate lithium ion battery cathode material having a low volume expansion ratio, so that the swelling degree can be effectively reduced when a soft package lithium ion battery is manufactured.
There is also a need in the art to provide a method for preparing the lithium iron manganese phosphate lithium ion battery cathode material, and a soft package lithium ion battery prepared from the cathode material.
Disclosure of Invention
An object of the present invention is to provide a lithium iron manganese phosphate lithium ion battery cathode material having a low volume expansion ratio, which can effectively reduce the degree of swelling when a soft pack lithium ion battery is manufactured.
The invention also aims to provide a preparation method of the lithium iron manganese phosphate lithium ion battery positive electrode material and a soft package lithium ion battery prepared from the positive electrode material.
Accordingly, a first aspect of the present invention is directed to a lithium iron manganese phosphate/carbon material having the general formula:
Li(Mn1-x-yFexMy)PO4/C
wherein:
0.1≤x≤0.45，0≤y≤0.1；
m is a divalent metal (doping element) selected from one or more of Mg, Co, Ca, Sc, Ni and Zn;
according to weight, the manganese lithium iron phosphate accounts for 97-99 wt% of the whole material, and the carbon accounts for 1.0-3 wt%;
it is prepared by the following method:
(i) providing a lithium iron manganese phosphate/carbon material;
(ii) mixing an aqueous solvent with the lithium iron manganese phosphate/carbon material for at least 10 minutes;
(iii) filtering and drying.
Another aspect of the invention relates to a method for preparing a lithium iron manganese phosphate/carbon material having the general formula:
Li(Mn1-x-yFexMy)PO4/C
wherein:
0.1≤x≤0.45，0≤y≤0.1；
m is a divalent metal (doping element) selected from one or more of Mg, Co, Ca, Sc, Ni and Zn;
according to weight, the manganese lithium iron phosphate accounts for 97-99 wt% of the whole material, and the carbon accounts for 1.0-3 wt%;
the method comprises the following steps:
(i) providing a lithium iron manganese phosphate/carbon material;
(ii) mixing an aqueous solvent with the lithium iron manganese phosphate material supported on carbon for at least 10 minutes;
(iii) filtering and drying.
The invention also relates to a soft package lithium ion battery which comprises the lithium iron manganese phosphate/carbon material as a positive electrode material.
Detailed Description
The inventor of the present invention has found that if the existing lithium iron manganese phosphate/carbon material is mixed with an aqueous solvent for at least 10 minutes, the volume expansion rate of the material can be significantly reduced. The present invention has been completed based on this finding.
In the present invention, the term "aqueous solvent" refers to water or a mixed solvent containing water, which may be a mixed solvent formed of water and one or more organic solvents selected from the following organic solvents in any ratio: water-soluble alcohols, such as methanol, ethanol, isopropanol; ketones, such as acetone, butanone; amides, such as N-methylpyrrolidone (NMP), N-Dimethylformamide (DMF), N-Dimethylacetamide (DMAC); sulfoxides, such as dimethyl sulfoxide (DMSO).
In one embodiment of the invention, the amount of water in the aqueous solvent is from 15 to 100% by weight, preferably from 20 to 95% by weight, more preferably from 25 to 90% by weight, and preferably from 30 to 85% by weight.
The lithium iron manganese phosphate/carbon material has the following general formula:
Li(Mn1-x-yFexMy)PO4/C
wherein:
the amount of iron, X, is 0.1 to 0.45, preferably 0.15 to 0.4, more preferably 0.2 to 0.35;
the amount Y of the doping element M is 0 to 0.1, preferably 0.02 to 0.09, more preferably 0.04 to 0.08;
the doping element M is a divalent metal and is selected from one or more of Mg, Co, Ca, Sc, Ni and Zn;
by weight, the lithium manganese iron phosphate accounts for 97-99 wt% of the whole material, preferably 97.5-98.5 wt%; carbon is present in an amount of 1.0 to 3% by weight, preferably 1.5 to 2.5% by weight.
In one embodiment of the invention, the lithium manganese iron phosphate is selected from LiMn0.55Fe0.45PO4、LiMn0.60Fe0.40PO4、LiMn0.60Fe0.35Mg0.05PO4、LiMn0.60Fe0.35Co0.05PO4、LiMn0.60Fe0.3Ni0.10PO4、LiMn0.65Fe0.3Zn0.10PO4、LiMn0.7Fe0.3PO4、LiMn0.70Fe0.25Mg0.05PO4、LiMn0.75Fe0.20Mg0.05PO4、LiMn0.75Fe0.25PO4、LiMn0.75Fe0.18Mg0.05Co0.02PO4、LiMn0.80Fe0.20PO4、LiMn0.85Fe0.15PO4Or a mixture of two or more thereof in any ratio.
The method for producing the lithium iron manganese phosphate/carbon material itself is not particularly limited, and may be a conventional production method known in the art, for example, a conventional hydrothermal method, a solid phase method, or the like.
In one embodiment of the present invention, the method for manufacturing lithium iron manganese phosphate/carbon includes the steps of:
(1) preparing pre-doped manganese oxalate;
-mixing a manganese source and a dopant compound containing a doping element to obtain a mixed powder;
-dissolving oxalic acid in water to obtain an oxalic acid solution;
reacting the mixed powder in the oxalic acid solution to obtain a manganese oxalate suspension containing doped elements;
filtering and drying the manganese oxalate turbid liquid to obtain pre-doped manganese oxalate;
(2) mixing an iron source, a lithium source, a phosphorus source, an organic carbon source and the pre-doped manganese oxalate with water, and mixing and grinding to obtain precursor slurry;
(3) drying and granulating the precursor slurry to obtain precursor powder;
(4) sintering the precursor powder under a protective atmosphere to obtain a sintered material;
(5) and crushing the sintered material to obtain the doped lithium iron manganese phosphate-carbon composite material.
In a preferred embodiment of the present invention, the method for manufacturing lithium iron manganese phosphate/carbon includes the steps of:
-adding manganese carbonate (manganese source) and a doping element compound to a mixer in a molar percentage ratio of doping element to manganese element and thoroughly mixing to preliminarily disperse the doping element compound in the manganese carbonate to obtain a mixed powder;
-heating water to 50-70 ℃, preferably about 55-65 ℃ in a reaction kettle and keeping the temperature; oxalic acid is then added to the water and thoroughly stirred to dissolve, obtaining an oxalic acid solution with a solute mass fraction of 25-35%, preferably about 30%. Keeping the temperature of the oxalic acid solution at about 50-70 ℃, preferably about 55-65 ℃, adding the mixed powder obtained in the previous step into the oxalic acid solution, and stirring for reaction; after the feeding is finished, continuously stirring for 1.5-2.5 hours, preferably 1.8-2.2 hours, so that the materials fully react until no bubbles are generated, and obtaining a doped manganese oxalate suspension;
filtering and dehydrating the manganese oxalate turbid liquid in a centrifugal machine until no filtrate flows out of a water outlet. Then drying by a double-cone dryer, wherein the drying temperature is 110-. Then naturally cooling, and discharging when the material temperature is lower than 50 ℃ to obtain the pre-doped manganese oxalate;
-adding the above pre-doped manganese oxalate, ferrous carbonate, lithium carbonate, ammonium dihydrogen phosphate and glucose together into water, stirring and mixing uniformly, and grinding in a sand mill to obtain a precursor slurry with a particle size D50 of about 2.5 μm;
drying and granulating the precursor slurry in centrifugal spray drying equipment to obtain precursor powder;
-sintering the precursor powder in a rotary furnace under a nitrogen atmosphere. The sintering is carried out in two stages, the working temperature of the first stage is 350-450 ℃, preferably 380-420 ℃, and the material retention time is 5-7 hours, preferably 5.5-6.5 hours; the second stage working temperature is 600-800 ℃, preferably 650-750 ℃, and the material retention time is 13-18 hours, preferably 14-16 hours. Then naturally cooling, and discharging when the temperature of the material is reduced to about 50 ℃ to obtain a sintered material;
and (4) crushing the sintered material in a jet mill to obtain the doped lithium iron manganese phosphate/carbon composite material.
The D50 particle size of the applicable lithium iron manganese phosphate-carbon composite material is between 1.0 and 15 mu m, preferably between 3.0 and 13 mu m, and more preferably between 5.0 and 10 mu m.
The method for manufacturing the lithium iron manganese phosphate/carbon composite material further comprises the step of mixing the obtained lithium iron manganese phosphate/carbon composite material with an aqueous solvent.
In one embodiment of the present invention, the mixing treatment with the aqueous solvent comprises stirring and mixing the lithium iron manganese phosphate/carbon composite material with the aqueous solvent for at least 10 minutes, for example, between 10 minutes and 10 hours, preferably between 15 minutes and 5 hours, and more preferably between 30 minutes and 2 hours.
In one embodiment of the present invention, the weight ratio of the lithium iron manganese phosphate/carbon material to the aqueous solvent during the mixing process is between 1:0.5 and 1:10, preferably between 1:1 and 1:5, and more preferably between 1:1.5 and 1: 3.
After mixing, the treated lithium iron manganese phosphate/carbon material can be dehydrated and dried. The dehydration and drying step to be applied is not particularly limited, and may be a conventional dehydration and drying step known in the art.
Non-limiting examples of suitable dewatering methods include, for example, atmospheric filtration, suction filtration, plate and frame filter pressing, belt filter pressing, mechanical centrifugation, and the like, and plate and frame filter pressing and mechanical centrifugation are preferred. Non-limiting examples of suitable drying methods are, for example, forced air oven drying, vacuum double cone drying, spin flash drying, coulter dryer, scraper dryer, inert atmosphere heat treatment, etc., preferably vacuum double cone drying. The atmosphere of the inert atmosphere heat treatment can be nitrogen, argon, carbon dioxide and mixed gas, and nitrogen is preferred; the heat treatment temperature is 120-700 ℃, preferably 150-600 ℃, more preferably 300-500 ℃; the heat treatment time is 30 minutes to 10 hours, preferably 1 hour to 6 hours, more preferably 2 hours to 4 hours.
In one embodiment of the present invention, the method for manufacturing the lithium iron manganese phosphate/carbon material comprises the steps of preparing the lithium iron manganese phosphate/carbon material by a conventional method, mixing the lithium iron manganese phosphate/carbon material with a water-methanol mixture, standing the mixture for 5 to 15 hours at normal temperature under continuous stirring, carrying out suction filtration, and drying the separated solid in a forced air oven at 50 to 70 ℃ for 10 to 15 hours to ensure complete drying. And transferring the dried material into an atmosphere furnace, treating the material for 20-40 minutes at the highest temperature of 600-750 ℃ in the argon atmosphere, and naturally cooling.
The present invention will be further described with reference to the following specific examples
Examples
The electrochemical performance test method comprises the following steps:
according to the active substance: conductive agent: mixing active substance, conductive carbon fiber and binder at weight ratio of 92:5:3 with NMP as solvent, and mixing at a ratio of about 10mg/cm2The surface density of (2) was double coated on aluminum foil and vacuum dried. After the pole piece is cut, the area density is about 6mg/cm2The artificial graphite cathode is a counter electrode, the concentration of lithium hexafluorophosphate is 1.2M, the solution of DMC (DMC: EC) is 1:1(V/V) is used as electrolyte, and a PP diaphragm with the thickness of 20 micrometers is used for isolating the positive electrode and the negative electrode, so that the 0.2Ah soft package battery is assembled. The cycle test was performed under the following conditions:
and (3) testing temperature: 23 +/-2 ℃;
voltage range: 2.5-4.2V;
the test flow comprises the following steps: charging: charging at 150mA/g, and stopping at 1.5mA/g constant voltage after 4.2V; discharging: after a release of 150mA/g active substance and a cut-off after 2.5V.
The volume of the pouch cells was measured using the drainage method before and after the cycle test.
Example 1
Preparation of LiMn according to the preparation of CN113148969A example 10.55Fe0.45PO4Material, carbon content 1.1% wt, D50 particle size 15 microns, this sample was designated B1. 1000g of this material was taken as a substrate and subjected to aqueous solvent treatment.
500g of a water-methanol mixture containing 25% of water was mixed with the lithium iron manganese phosphate material, left to stand at normal temperature for 10 hours under continuous stirring, then filtered with suction, and the separated solid was dried in a forced air oven at 60 ℃ for 12 hours to ensure complete drying. And transferring the dried material into an atmosphere furnace, processing the material for 30 minutes at the highest temperature of 700 ℃ in an argon atmosphere, and naturally cooling the material. The treated material was designated as S1.
Electrochemical performance tests were performed on each of B1 and S1 in the manner described above, and the blade fineness values of the coating slurries were recorded, and the results are shown in the following tables.
From the results, the treated material has the advantages of finer slurry granularity, shorter cycle life and less gas generation of the battery, more excellent comprehensive performance than the material before treatment, and more importantly, the volume expansion rate of the soft package battery is obviously reduced.
Example 2
Preparation of LiMn according to the preparation of CN113148969A example 10.60Fe0.40PO4Material, carbon content 1.5% wt. After jet milling the material, the material had a D50 particle size of 1.0 micron, and this sample was designated B2. 1000g of this material was taken as a substrate and subjected to aqueous solvent treatment.
750g of a water-ethanol mixture having a water content of 50% was mixed with the above lithium iron manganese phosphate material, left to stand at normal temperature for 5 hours with continuous stirring, and then centrifuged, and the separated solid was dried in a vacuum oven at 80 ℃ for 6 hours to ensure complete drying. And transferring the dried material into an atmosphere furnace, treating the material for 5 hours at the highest temperature of 600 ℃ in a nitrogen atmosphere, and naturally cooling the material. The treated material was designated as S2.
Electrochemical performance tests were performed on each of B2 and S2 in the manner described above, and the blade fineness values of the coating slurries were recorded, and the results are shown in the following tables.
The conclusion of example 2 is similar to that of example 1, and the material treated by the aqueous solvent has better performance.
Example 3
Doped LiMn was prepared according to the method of CN113148969A example 10.60Fe0.35Mg0.05PO4The material, having a carbon content of 2.0% wt, had a D50 particle size of 10 microns, and this sample was designated B3. 1000g of this material was taken as a substrate and subjected to aqueous solvent treatment.
1000g of a water-acetone mixture with a water content of 75% and a lithium iron manganese phosphate material are mixed, placed for 2 hours at normal temperature under continuous stirring, then centrifuged, and the separated solid is placed in a 100 ℃ double cone dryer for drying for 2 hours to ensure complete drying. And transferring the dried material into an atmosphere furnace, processing for 7 hours at the highest temperature of 500 ℃ in a nitrogen atmosphere, and naturally cooling. The treated material was designated as S3.
Electrochemical performance tests were performed on B3 and S3, respectively, as described above, and the blade fineness values of the coating slurries were recorded, with the results shown in the following table that S3 performance was significantly better than B3.
Example 4
Doped LiMn was prepared according to the method of CN113148969A example 10.60Fe0.35Co0.05PO4The material, having a carbon content of 2.5% wt, had a D50 particle size of 7.8 microns, and this sample was designated B4. 1000g of this material was taken as a substrate and subjected to aqueous solvent treatment.
1500g of a water-DMF mixture containing 60% water was mixed with lithium iron manganese phosphate material, left to stand at 50 ℃ for 1 hour with constant stirring, then centrifuged and the separated solid was dried in a vacuum oven at 90 ℃ for 6 hours to ensure complete drying. And transferring the dried material into an atmosphere furnace, treating the material for 10 hours at the highest temperature of 400 ℃ in a nitrogen atmosphere, and naturally cooling the material. The treated material was designated as S4.
Electrochemical performance tests were performed on each of B4 and S4 in the manner described above, and the blade fineness values of the coating slurries were recorded, and the results are shown in the following tables.
Example 5
Doped LiMn was prepared according to the method of CN113148969A example 10.60Fe0.3Ni0.10PO4The material, having a carbon content of 3.0% wt, had a D50 particle size of 2 microns, and this sample was designated B5. 1000g of this material was taken as a substrate and subjected to aqueous solvent treatment.
2000g of a water-DMAc mixture containing 70% water was mixed with a lithium iron manganese phosphate material, left for 30 minutes at 50 ℃ with constant stirring, then press filtered, and the separated solid was dried in a 110 ℃ double cone dryer for 2.5 hours to ensure complete drying. And transferring the dried material into an atmosphere furnace, treating the material for 5 hours at the highest temperature of 400 ℃ in a nitrogen atmosphere, and naturally cooling the material. The treated material was designated as S5.
Electrochemical performance tests were performed on each of B5 and S5 in the manner described above, and the blade fineness values of the coating slurries were recorded, and the results are shown in the following tables.
Example 6
Doped LiMn was prepared according to the method of CN113148969A example 10.65Fe0.3Zn0.10PO4The material, having a carbon content of 2.0% wt, had a D50 particle size of 3 microns, and this sample was designated B6. 1000g of this material was taken as a substrate and subjected to aqueous solvent treatment.
2500g of a water-DMSO mixture having a water content of 60% was mixed with a lithium iron manganese phosphate material, left for 30 minutes at 50 ℃ with constant stirring, then filter-pressed, and the separated solid was dried in a 120 ℃ double cone dryer for 3 hours to ensure complete drying. And transferring the dried material into an atmosphere furnace, processing for 4 hours at the highest temperature of 300 ℃ in a nitrogen atmosphere, and naturally cooling. The treated material was designated as S6.
Electrochemical performance tests were performed on each of B6 and S6 in the manner described above, and the blade fineness values of the coating slurries were recorded, and the results are shown in the following tables.
Example 7
Preparation of LiMn according to the preparation of CN112110433A example 10.7Fe0.3PO4The material, having a carbon content of 1.7% wt, had a D50 particle size of 9 microns, and this sample was designated B7. 1000g of this material was taken as a substrate and subjected to aqueous solvent treatment.
2000g of water and the lithium iron manganese phosphate material are mixed, placed for 2 hours at normal temperature under continuous stirring, then centrifuged, and the separated solid is placed in a 90 ℃ double cone dryer for drying for 2 hours to ensure complete drying. And transferring the dried material into an atmosphere furnace, processing for 4 hours at the highest temperature of 200 ℃ in a nitrogen atmosphere, and naturally cooling. The treated material was designated as S7.
Electrochemical performance tests were performed on each of B7 and S7 in the manner described above, and the blade fineness values of the coating slurries were recorded, and the results are shown in the following tables.
Example 8
Doped LiMn was prepared according to the method of CN113148969A example 10.70Fe0.25Mg0.05PO4The material, having a carbon content of 1.5% wt, had a D50 particle size of 10 microns, and this sample was designated B7. 1000g of this material was taken as a substrate and subjected to aqueous solvent treatment.
2000g of a water-NMP mixture having a water content of 75% and a lithium iron manganese phosphate material were mixed, left to stand at room temperature for 2 hours with continuous stirring, and then centrifuged, and the separated solid was dried in a 120 ℃ double cone dryer for 3 hours to ensure complete drying. And transferring the dried material into an atmosphere furnace, treating for 8 hours at the highest temperature of 150 ℃ in a carbon dioxide atmosphere, and naturally cooling. The treated material was designated as S8.
Electrochemical performance tests were performed on each of B8 and S8 in the manner described above, and the blade fineness values of the coating slurries were recorded, and the results are shown in the following tables.
Example 9
Doped LiMn was prepared according to the method of CN113148969A example 10.70Fe0.25Mg0.05PO4The material, having a carbon content of 1.5% wt, was crushed to give a sample of D50 having a particle size of 2 microns, which was designated B9. 1000g of this material was taken as a substrate and subjected to aqueous solvent treatment.
2000g of a water-NMP mixture having a water content of 75% and a lithium iron manganese phosphate material were mixed, left to stand at room temperature for 2 hours with continuous stirring, and then centrifuged, and the separated solid was dried in a 120 ℃ double cone dryer for 3 hours to ensure complete drying. And transferring the dried material into an atmosphere furnace, treating for 8 hours at the highest temperature of 150 ℃ in a carbon dioxide atmosphere, and naturally cooling. The treated material was designated as S9.
Electrochemical performance tests were performed on each of B9 and S9 in the manner described above, and the blade fineness values of the coating slurries were recorded, and the results are shown in the following tables.
Example 10
Preparation of LiMn according to the preparation of CN112110433A example 10.75Fe0.25PO4Material, carbon content 2.0% wt, gave a sample of D50 particle size 10 microns, which was designated B10. 1000g of this material was taken as a substrate and subjected to aqueous solvent treatment.
2000g of a water-NMP mixture containing 80% of water and a lithium iron manganese phosphate material were mixed, left at room temperature for 1 hour with constant stirring, and then centrifuged, and the separated solid was dried in a 100 ℃ double cone dryer for 5 hours to ensure complete drying. And transferring the dried material into an atmosphere furnace, treating for 8 hours at the highest temperature of 150 ℃ in a carbon dioxide atmosphere, and naturally cooling. The treated material was designated as S10.
Electrochemical performance tests were performed on each of B10 and S10 in the manner described above, and the blade fineness values of the coating slurries were recorded, and the results are shown in the following tables.
Example 11
Doped LiMn was prepared according to the method of CN113148969A example 10.75Fe0.18Mg0.05Co0.02PO4Material with a carbon content of 1.9% wt, to obtainA sample of D50 with a particle size of 10 microns was designated B11. 1000g of this material was taken as a substrate and subjected to aqueous solvent treatment.
1500g of water and a lithium iron manganese phosphate material were mixed, left for 15 minutes at 50 ℃ with constant stirring, then pressure filtered, and the separated solids were dried in a 100 ℃ double cone dryer for 2 hours to ensure complete drying. And transferring the dried material into an atmosphere furnace, treating for 4 hours at the highest temperature of 200 ℃ in the atmosphere of carbon dioxide, and naturally cooling. The treated material was designated as W11.
1500g of a water-NMP mixture containing 80% water was mixed with a lithium iron manganese phosphate material, left for 15 minutes at 50 ℃ with constant stirring, then filter-pressed, and the separated solid was dried in a 100 ℃ double cone dryer for 2 hours to ensure complete drying. And transferring the dried material into an atmosphere furnace, treating for 4 hours at the highest temperature of 200 ℃ in the atmosphere of carbon dioxide, and naturally cooling. The treated material was designated as S11.
Electrochemical performance tests were performed on each of B11, W11, and S11 in the manner described above, and the blade fineness values of the coating slurries were recorded, and the results are shown in the following tables.
The test results show that the volume expansion rate of the soft package battery is the minimum when the mixed solvent is used for treatment, the volume expansion rate of the soft package battery after pure water treatment is the second, and the volume expansion rate of the soft package battery of the untreated composite material is the maximum.
Example 12
A sample of B10 from the example was taken and is designated herein as B11. 1000g of this material was taken as a substrate and subjected to aqueous solvent treatment.
3000g of water and a lithium iron manganese phosphate material are mixed, placed for 15 minutes at 50 ℃ under continuous stirring, then subjected to pressure filtration, and the separated solid is placed in a 100 ℃ double cone dryer for drying for 2 hours to ensure complete drying. And transferring the dried material into an atmosphere furnace, treating for 4 hours at the highest temperature of 200 ℃ in the atmosphere of carbon dioxide, and naturally cooling. The treated material was designated as S12.
Electrochemical performance tests were performed on each of B12 and S12 in the manner described above, and the blade fineness values of the coating slurries were recorded, and the results are shown in the following tables.
Example 13
Preparation of LiMn according to the preparation of CN113148969A example 10.80Fe0.20PO4Material, carbon content 3.0% wt, gave a sample of D50 particle size 8 microns, which was designated B13. 1000g of this material was taken as a substrate and subjected to aqueous solvent treatment.
1500g of pure water and lithium manganese iron phosphate material were mixed, left for 10 minutes at 50 ℃ with constant stirring, then press-filtered, and the separated solids were dried in a 100 ℃ double cone dryer for 2 hours to ensure complete drying. And transferring the dried material into an atmosphere furnace, treating the material at the highest temperature of 120 ℃ for 10 hours in a nitrogen atmosphere, and then naturally cooling the material. The treated material was designated as S13.
Electrochemical performance tests were performed on each of B13 and S13 in the manner described above, and the blade fineness values of the coating slurries were recorded, and the results are shown in the following tables.
Example 14
Preparation of LiMn according to the preparation of CN113148969A example 10.85Fe0.15PO4Material, carbon content 2.3% wt, gave a sample of D50 particle size 5 microns, which was designated B14. 1000g of this material was taken as a substrate and subjected to aqueous solvent treatment.
3000g of water and a lithium iron manganese phosphate material are mixed, placed for 15 minutes at 50 ℃ under continuous stirring, then subjected to pressure filtration, and the separated solid is placed in a 100 ℃ double cone dryer for drying for 2 hours to ensure complete drying. And transferring the dried material into an atmosphere furnace, treating the material for 5 hours at the highest temperature of 120 ℃ in a nitrogen atmosphere, and naturally cooling the material. The treated material was designated as S14.
Electrochemical performance tests were performed on each of B14 and S14 in the manner described above, and the blade fineness values of the coating slurries were recorded, and the results are shown in the following tables.
Claims (10)
1. A lithium iron manganese phosphate/carbon material having the general formula:
Li(Mn1-x-yFexMy)PO4/C
wherein:
0.1≤x≤0.45，0≤y≤0.1；
the doping element M is a divalent metal and is selected from one or more of Mg, Co, Ca, Sc, Ni and Zn;
according to weight, the manganese lithium iron phosphate accounts for 97-99 wt% of the whole material, and the carbon accounts for 1.0-3 wt%;
it is prepared by the following method:
(i) providing a lithium iron manganese phosphate/carbon material;
(ii) mixing an aqueous solvent with the lithium iron manganese phosphate/carbon material for at least 10 minutes;
(iii) filtering and drying.
2. The lithium iron manganese phosphate/carbon material of claim 1 selected from the group consisting of LiMn0.55Fe0.45PO4、LiMn0.60Fe0.40PO4、LiMn0.60Fe0.35Mg0.05PO4、LiMn0.60Fe0.35Co0.05PO4、LiMn0.60Fe0.3Ni0.10PO4、LiMn0.65Fe0.3Zn0.10PO4、LiMn0.7Fe0.3PO4、LiMn0.70Fe0.25Mg0.05PO4、LiMn0.75Fe0.20Mg0.05PO4、LiMn0.75Fe0.25PO4、LiMn0.75Fe0.18Mg0.05Co0.02PO4、LiMn0.80Fe0.20PO4、LiMn0.85Fe0.15PO4Or a mixture of two or more thereof in any ratio.
3. The lithium iron manganese phosphate/carbon material according to claim 1 or 2, wherein the aqueous solvent is selected from the group consisting of water and an aqueous mixture comprising water and one or more organic solvents selected from the group consisting of water-soluble alcohols, ketones, amides, and sulfoxides.
4. The lithium iron manganese phosphate/carbon material according to claim 3, wherein said organic solvent is selected from the group consisting of methanol, ethanol, isopropanol, acetone, methyl ethyl ketone, N-methyl pyrrolidone (NMP), N, N-Dimethylformamide (DMF), N, N-Dimethylacetamide (DMAC), and Dimethylsulfoxide (DMSO).
5. The lithium iron manganese phosphate/carbon material according to claim 3, wherein the amount of water in said aqueous solvent is 15 to 100 wt%, preferably 20 to 95 wt%, more preferably 25 to 90 wt%, and preferably 30 to 85 wt%.
6. The lithium iron manganese phosphate/carbon material according to claim 1 or 2, characterized in that an aqueous solvent is mixed with the lithium iron manganese phosphate/carbon material for between 10 minutes and 10 hours, preferably for between 15 minutes and 5 hours, more preferably for between 30 minutes and 2 hours.
7. A preparation method of a lithium iron manganese phosphate/carbon material with the following general formula:
Li(Mn1-x-yFexMy)PO4/C
wherein:
0.1≤x≤0.45，0≤y≤0.1；
the doping element M is a divalent metal and is selected from one or more of Mg, Co, Ca, Sc, Ni and Zn;
according to weight, the manganese lithium iron phosphate accounts for 97-99 wt% of the whole material, and the carbon accounts for 1.0-3 wt%;
the method comprises the following steps:
(i) providing a lithium iron manganese phosphate/carbon-loaded material;
(ii) mixing an aqueous solvent with the lithium iron manganese phosphate material supported on carbon for at least 10 minutes;
(iii) filtering and drying.
8. The method of claim 7, wherein the aqueous solvent is selected from the group consisting of water and aqueous mixtures comprising water and one or more organic solvents selected from the group consisting of water-soluble alcohols, ketones, amides, and sulfoxides.
9. The method according to claim 8, wherein the organic solvent is selected from the group consisting of methanol, ethanol, isopropanol, acetone, butanone, N-methylpyrrolidone (NMP), N, N-Dimethylformamide (DMF), N, N-Dimethylacetamide (DMAC), and Dimethylsulfoxide (DMSO).
10. A soft-packed lithium ion battery comprising the lithium iron manganese phosphate/carbon material according to any one of claims 1 to 6 as a positive electrode material.
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