CN114975986A - High-performance lithium iron manganese phosphate cathode material and preparation method thereof - Google Patents
High-performance lithium iron manganese phosphate cathode material and preparation method thereof Download PDFInfo
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- CN114975986A CN114975986A CN202210785768.9A CN202210785768A CN114975986A CN 114975986 A CN114975986 A CN 114975986A CN 202210785768 A CN202210785768 A CN 202210785768A CN 114975986 A CN114975986 A CN 114975986A
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- iron manganese
- lithium iron
- manganese phosphate
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- lithium
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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 60
- 239000010406 cathode material Substances 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000000463 material Substances 0.000 claims abstract description 97
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 31
- 239000002245 particle Substances 0.000 claims abstract description 28
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 15
- 239000011164 primary particle Substances 0.000 claims abstract description 15
- 239000010405 anode material Substances 0.000 claims abstract description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 25
- 239000011572 manganese Substances 0.000 claims description 22
- 238000010438 heat treatment Methods 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 17
- 239000002244 precipitate Substances 0.000 claims description 14
- SNKMVYBWZDHJHE-UHFFFAOYSA-M lithium;dihydrogen phosphate Chemical compound [Li+].OP(O)([O-])=O SNKMVYBWZDHJHE-UHFFFAOYSA-M 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- 239000007774 positive electrode material Substances 0.000 claims description 12
- 150000003839 salts Chemical class 0.000 claims description 12
- 238000001354 calcination Methods 0.000 claims description 11
- 230000001376 precipitating effect Effects 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 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 claims description 10
- 239000008103 glucose Substances 0.000 claims description 10
- 239000011734 sodium Substances 0.000 claims description 9
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 claims description 9
- 229940039790 sodium oxalate Drugs 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 8
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 5
- 229940039748 oxalate Drugs 0.000 claims description 5
- 238000004321 preservation Methods 0.000 claims description 4
- 238000010298 pulverizing process Methods 0.000 claims description 3
- 229910015645 LiMn Inorganic materials 0.000 claims description 2
- 229920002472 Starch Polymers 0.000 claims description 2
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 2
- 229930006000 Sucrose Natural products 0.000 claims description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- 150000001720 carbohydrates Chemical class 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 150000003891 oxalate salts Chemical class 0.000 claims description 2
- 230000001681 protective effect Effects 0.000 claims description 2
- 239000008107 starch Substances 0.000 claims description 2
- 235000019698 starch Nutrition 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 239000005720 sucrose Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims 1
- 230000008901 benefit Effects 0.000 abstract description 4
- 238000003756 stirring Methods 0.000 description 29
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 239000011248 coating agent Substances 0.000 description 9
- 238000000576 coating method Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- 230000001276 controlling effect Effects 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- 238000001914 filtration Methods 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- 238000010902 jet-milling Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000007873 sieving Methods 0.000 description 6
- 239000000843 powder Substances 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 4
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000011858 nanopowder Substances 0.000 description 3
- 229910000616 Ferromanganese Inorganic materials 0.000 description 2
- 229910010710 LiFePO Inorganic materials 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 238000009831 deintercalation Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical compound [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 229910010776 LiFexMn Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000013098 chemical test method Methods 0.000 description 1
- 238000010280 constant potential charging Methods 0.000 description 1
- 238000010277 constant-current charging Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 150000002696 manganese Chemical class 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- YQCIWBXEVYWRCW-UHFFFAOYSA-N methane;sulfane Chemical compound C.S YQCIWBXEVYWRCW-UHFFFAOYSA-N 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000010450 olivine Substances 0.000 description 1
- 229910052609 olivine Inorganic materials 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000013031 physical testing Methods 0.000 description 1
- -1 polyethylene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 230000002195 synergetic effect Effects 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
- H01M4/48—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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—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
-
- 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
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention belongs to the technical field of lithium ion battery materials, and particularly relates to a high-performance lithium iron manganese phosphate cathode material and a preparation method thereof. In order to enable the lithium manganese iron phosphate anode material to have excellent electrochemical performance and cycle performance, the relation between the primary particle granularity of the anode material, namely the D50 value a, the carbon content value b and the element doping amount z is limited to be 0.5-100 xbz/(a + b) -1.3, under the condition that the granularity, the carbon content and the element doping amount of the material particles have a better matching degree, the lithium manganese iron phosphate material can give consideration to excellent electrochemical performance and cycle performance, the electrochemical performance of the lithium manganese iron phosphate is favorably improved, and the lithium manganese iron phosphate anode material has the advantages of being simple and easy to operate.
Description
Technical Field
The invention belongs to the technical field of lithium ion battery materials, and particularly relates to a high-performance lithium iron manganese phosphate cathode material and a preparation method thereof.
Background
In recent years, the development of the electric automobile industry is greatly supported by the nation, so that the requirements of automobile enterprises on battery enterprises are increased day by day, and a positive electrode material and a battery with high specific energy, long service life and low cost are urgently needed. Lithium ion batteries are widely used due to their advantages of high operating voltage, high specific energy, long cycle life, low pollution, etc.
Among conventional cathode materials, phosphate cathode materials have attracted considerable attention as potential substitutes for commercial layered cathode materials due to their advantages in structural stability, cost-effectiveness, and environmental friendliness. Since 1997, LiFePO of olivine structure 4 Has received much attention and research because of its relatively high theoretical capacity (170mAh/g), high safety and low cost. However, it is compatible with low cell voltages (3.4Vvs. Li/Li) + ) The associated energy density limits its use in electric vehicles. Although LiMnPO 4 Due to higher working voltage Mn 3+ /Mn 2+ (4.1Vvs.Li/Li + ) Comparative Fe 3+ /Fe 2+ About 20% higher than LiFePO 4 Has a higher energy density, however, LiMnPO 4 Is an insulator having an energy band gap of about 2eV, and the John-Teller effect inevitably occurs because LiMnPO 4 /MnPO 4 The interface during charge/discharge creates a large kinetic barrier for ion and electron transport, resulting in low electron conductivity. At present, LiFePO 4 Is considered to be a semiconductor having an energy band gap of about 0.3 eV. With LiFePO 4 (10-8S/cm) LiMnPO 4 (<10 - 10 S/cm) is much lower, resulting in poorer electrochemical performance. In recent years, attempts have been made to reduce the particle size, coat an electron conductive agent, or dope Mg 2+ 、Fe 2+ 、Cu 2+ 、Co 2+ 、Ni 2+ 、Ca 2+ Increasing LiMnPO by isocationation 4 The electronic conductivity of the material. Wherein, the reduction of the particle size can reduce the transmission distance of electrons and lithium ions, thereby improving the rate capability; the surface conductivity can be increased by coating with the electronic conductive agent; cationic polymerSub-doping is also considered an important method because it can introduce defects into the crystal lattice, thereby greatly improving the conductivity of the material. At present, the solid solution LiFexMn can work under the voltage of 2.0-4.35V 1-x PO 4 Is considered to be a promising alternative, mainly thanks to the incorporation of LiFePO in solid solution 4 Relatively high electron conductivity and LiMnPO 4 The advantage of a relatively high voltage.
At present, the preparation methods of lithium iron manganese phosphate materials are mainly divided into two types: one is that manganese salt, iron salt, lithium salt, phosphoric acid and carbon source are dissolved in water and are prepared by hydrothermal reaction in a high-pressure reaction kettle, such as the hydrothermal method disclosed in the Chinese patent CN 114335469A; however, a method similar to the method for producing lithium iron phosphate is commonly used in industry, for example, the ball milling method disclosed in chinese patent CN113929073A is obtained by adding ferromanganese phosphate or ferromanganese oxalate, a phosphorus source, a carbon source, and a dopant into water, stirring, mixing and sanding, spray-drying the sanded liquid, and calcining. However, in any preparation method, higher requirements are put on the performance of the lithium iron manganese phosphate material.
Disclosure of Invention
Therefore, the technical problem to be solved by the invention is to provide a high-performance lithium manganese iron phosphate positive electrode material, which can enable the lithium manganese iron phosphate material to have both excellent electrochemical performance and cycle performance by reasonably matching the primary particle size, element doping amount and carbon coating amount of the lithium manganese iron phosphate material;
the second technical problem to be solved by the invention is to provide a preparation method and application of the lithium iron manganese phosphate anode material.
In order to solve the technical problems, the invention discloses a high-performance lithium iron manganese phosphate positive electrode material which is provided with LiMn x Fe y M z PO 4 The chemical structure shown;
wherein, the M element is at least one of Cr, Ti, Mg, Ni, Co, Cu and Zn elements;
the parameters satisfy the following relations: x + y + z is equal to 1, x is more than or equal to 0.5 and less than or equal to 0.8, z is more than or equal to 0.005 and less than or equal to 0.02, a is more than or equal to 0.05 and less than or equal to 0.5, and b is more than or equal to 1 and less than or equal to 2.5;
the primary particle size D50 value a of the positive electrode material is 0.05-0.5 mu m, and the carbon content value b is 1-2.5 wt%.
In the cathode material of the invention, the value of D50 of the primary particles of the material can be regulated and controlled by adjusting the calcination temperature of the material, and generally, the higher the calcination temperature is, the larger the value of D50 is.
Preferably, the element doping amount z, the primary particle size D50 value a and the carbon content value b of the cathode material satisfy the following relationship: 0.5 is less than or equal to 100 xbz/(a + b) is less than or equal to 1.3.
The invention also discloses a method for preparing the high-performance lithium iron manganese phosphate cathode material, which comprises the following steps of:
(1) dissolving soluble oxalate in water, and adding soluble Fe 2+ Salt and soluble Mn 2+ Salt, reacting to form FeMnC 2 O 4 Precipitating and collecting precipitate;
(2) taking lithium dihydrogen phosphate LiH 2 PO 4 With said FeMnC 2 O 4 Precipitating and mixing, and adding a doping compound and a carbon source material according to the selected doping elements for mixing to obtain a mixed material;
(3) and calcining the obtained mixed material in a protective atmosphere to obtain the catalyst.
Specifically, in the step (1), the soluble oxalate and the soluble Fe are adopted 2+ Salt and soluble Mn 2+ The molar ratio of the salt is 1: x: 1-x, wherein x is 0.2-0.5.
Preferably, the soluble oxalate salt comprises sodium oxalate, Na 2 C 2 O 4 、K 2 C 2 O 4 Or (NH) 4 ) 2 C 2 O 4 ；
Preferably, the soluble Fe 2+ The salt comprising FeCl 2 Or FeSO 4 ；
Preferably, the soluble Mn is 2+ The salt comprises MnCl 2 Or MnSO 4 。
In particular, the followingIn the step (2), the lithium dihydrogen phosphate LiHPO 4 、FeMnC 2 O 4 The molar ratio of the precipitated and doped compound to glucose is 1: (1-z): z: 0.021-0.055, wherein z is 0.005-0.02.
Preferably, the doping compound comprises an oxide and/or hydroxide of a doping element;
preferably, the carbon source material includes a saccharide, and more preferably, the carbon source material includes glucose, sucrose or starch.
Specifically, the preparation method of the high-performance lithium iron manganese phosphate cathode material comprises the following steps of (2):
the lithium dihydrogen phosphate LiH 2 PO 4 The particle diameter of (A) is 1-2 μm;
the particle size of the doping compound is 20-30 nm.
Specifically, the step (2) further comprises the step of crushing the obtained mixed material to the particle size of 300-400 nm. Preferably, the crushing step is a jet mill crushing treatment, and the crushing particle size can be adjusted by adjusting equipment parameters according to different equipment.
Specifically, in the step (3), the temperature of the calcination step is 350-700 ℃;
preferably, the calcining step comprises: heating to 350-400 ℃ at the speed of 1-3 ℃/min for heat preservation for 3-5h, and continuing heating to 600-700 ℃ at the speed of 1-3 ℃/min for heat preservation for 10-15 h.
The invention also discloses the application of the lithium iron manganese phosphate anode material or the lithium iron manganese phosphate anode material prepared by the method in preparing a lithium ion battery anode or a lithium ion battery.
The invention also discloses a lithium ion battery anode or a lithium ion battery prepared from the lithium iron manganese phosphate anode material or the lithium iron manganese phosphate anode material prepared by the method.
In the research, the main factors influencing the performance of the lithium iron manganese phosphate anode material disclosed by the invention comprise the primary particle size of the material. The carbon coating amount and the doping amount of doping elements, wherein the primary particle size is too large, so that the lithium ion deintercalation is difficult to influence, and the rate capability is poor; the specific capacity of the material is influenced by over-high doping, and the electronic conductivity and the cycle performance of the material are influenced by the amount of carbon coating. Therefore, in order to enable the lithium manganese iron phosphate to have excellent electrochemical performance and cycle performance, the relation between the primary particle granularity of the positive electrode material, the carbon content value b and the element doping amount z is limited to be a D50 value a, and the relation between 0.5-100 xbz/(a + b) -1.3 is met, so that the granularity, the carbon content and the element doping amount of the material particles can have a better matching degree under the condition of the proportion, the lithium manganese iron phosphate material can give consideration to excellent electrochemical performance and cycle performance, the electrochemical performance of the lithium manganese iron phosphate is favorably improved, and the operation is simple and easy to implement.
In the anode material, the doping amount of elements is not easy to be too much or too little, and experiments show that the size of primary particles and the doping amount of elements are in a direct proportion relationship in a certain range. When the primary particle size is increased, the transmission path of electrons and lithium ions in the particles is lengthened, so that some necessary elements need to be doped to improve the electronic conductivity and the ionic conductivity of the material, so as to ensure the exertion of the capacity of the material. Although the carbon coating treatment can improve the electron conductivity of the material, the carbon coating amount is not too large, and if the carbon coating amount is too large, the carbon coating thickness will be increased to hinder the lithium ion deintercalation, and the specific surface area of the material is increased, which is not favorable for the processability of the material. The conductivity of the material is reduced when the primary particle size is too large, the cycling stability and the processing performance of the material are not facilitated when the primary particle size is too small, and the proper primary particle size can be regulated and controlled by controlling the calcination temperature. Therefore, the positive electrode material disclosed by the invention can effectively ensure that the lithium iron manganese phosphate material has both excellent electrochemical performance and excellent cycle performance by reasonably matching the granularity, the carbon content and the element doping amount.
Detailed Description
Example 1
1mol of sodium oxalate Na 2 C 2 O 4 Adding 3.5L of water, stirring until the mixture is completely dissolved, and then adding 0.4mol of FeCl 2 And 0.6mol of MnCl 2 The Fe can be formed by fully and uniformly mixing the materials through ultrasonic stirring 0.4 Mn 0.6 C 2 O 4 Precipitating, collecting precipitate, filtering, washing, and vacuum drying.
Taking 1mol of lithium dihydrogen phosphate with the particle diameter of 1-2 μm and 0.9875mol of the Fe 0.4 Mn 0.6 C 2 O 4 The precipitates were mixed and then 0.00625mol of Cr was added 2 O 3 And (3) fully stirring the nano powder (with the particle size of 20-30nm) and 0.03817mol of glucose in a high-speed stirrer to obtain a mixed material. And (3) performing jet milling on the mixed material, controlling the crushing particle size to reach 300-400nm, collecting the crushed mixed material, stirring the mixed material in a high-speed stirrer at 2000rpm for 1h, and fully and uniformly mixing the material.
And heating the fully mixed materials to 400 ℃ at the speed of 2 ℃/min under the protection of nitrogen, preserving heat for 4h, then continuously heating to 670 ℃ at the speed of 2 ℃/min, preserving heat for 10h, then naturally cooling, and crushing the obtained lithium manganese iron phosphate to D50, sieving the D50 on a 1-2 mu m sieve of 400 meshes, thereby obtaining the lithium manganese iron phosphate material.
Example 2
1mol of sodium oxalate Na 2 C 2 O 4 Adding into 4L water, stirring to dissolve completely, and adding 0.4mol FeCl 2 And 0.6mol of MnCl 2 Fully stirring the mixture by ultrasonic to form Fe 0.4 Mn 0.6 C 2 O 4 Precipitating, filtering and washing the precipitate, drying in vacuum and collecting for later use.
1mol of lithium dihydrogen phosphate with the grain diameter of 1-2 mu m and 0.99mol of Fe 0.4 Mn 0.6 C 2 O 4 The precipitates were mixed and then 0.01mol of Co (OH) was added 2 Stirring nanometer powder (20-30nm) and 0.03273mol of glucose in a high-speed stirrer to obtain a mixed material. And (3) performing jet milling on the mixed material, controlling the crushing particle size to reach 300-400nm, collecting the crushed mixed material, stirring the mixed material in a high-speed stirrer at 2000rpm for 1h, and fully and uniformly mixing the materials.
And heating the fully mixed materials to 400 ℃ at the speed of 2 ℃/min under the protection of nitrogen, preserving heat for 4h, then continuously heating to 650 ℃ at the speed of 2 ℃/min, preserving heat for 10h, then naturally cooling, and crushing the obtained lithium manganese iron phosphate to D50, sieving the D50 on a screen of 1-2 mu m and 400 meshes, thereby obtaining the lithium manganese iron phosphate material.
Example 3
1mol of sodium oxalate Na 2 C 2 O 4 Adding 4L of water, stirring to dissolve, and then adding 0.4mol of FeCl 2 And 0.6mol of MnCl 2 Ultrasonic stirring to form Fe 0.4 Mn 0.6 C 2 O 4 Precipitating, filtering and washing the precipitate, drying in vacuum and collecting for later use.
1mol of lithium dihydrogen phosphate with the grain diameter of 1-2 mu m and 0.985mol of Fe 0.4 Mn 0.6 C 2 O 4 Mixing, then adding 0.015mol of Co (OH) 2 Stirring nanometer powder (20-30nm) and 0.04365mol of glucose in a high-speed stirrer to obtain a mixed material. And (3) performing jet milling on the mixed material, controlling the crushing particle size to reach 300-400nm, collecting the crushed mixed material, stirring the mixed material in a high-speed stirrer at 2000rpm for 1h, and fully and uniformly mixing the materials.
And heating the fully mixed material to 400 ℃ at the speed of 2 ℃/min under the protection of nitrogen, preserving heat for 4h, continuously heating to 690 ℃ at the speed of 2 ℃/min, preserving heat for 10h, then naturally cooling, and crushing the obtained lithium manganese iron phosphate to D50, sieving the D50 on a screen of 1-2 mu m and 400 meshes to obtain the lithium manganese iron phosphate material.
Example 4
1mol of sodium oxalate Na 2 C 2 O 4 Adding 3.5L of water, stirring until the mixture is completely dissolved, and then adding 0.3mol of FeCl 2 And 0.7mol of MnCl 2 The Fe can be formed by fully and uniformly mixing the materials through ultrasonic stirring 0.3 Mn 0.7 C 2 O 4 Precipitating, collecting precipitate, filtering and washing, and vacuum drying for later use.
Taking 1mol of lithium dihydrogen phosphate with the particle diameter of 1-2 mu mWith 0.987mol of Fe as described above 0.4 Mn 0.6 C 2 O 4 The precipitates were mixed, followed by addition of 0.013mol of Co (OH) 2 And (3) fully stirring the nano powder (with the particle size of 20-30nm) and 0.03817mol of glucose in a high-speed stirrer to obtain a mixed material. And (3) performing jet milling on the mixed material, controlling the crushing particle size to reach 300-400nm, collecting the crushed mixed material, stirring the mixed material in a high-speed stirrer at 2000rpm for 1h, and fully and uniformly mixing the material.
And heating the fully mixed materials to 400 ℃ at the speed of 2 ℃/min under the protection of nitrogen, preserving heat for 4h, then continuously heating to 670 ℃ at the speed of 2 ℃/min, preserving heat for 10h, then naturally cooling, and crushing the obtained lithium manganese iron phosphate to D50, sieving the D50 on a 1-2 mu m sieve of 400 meshes, thereby obtaining the lithium manganese iron phosphate material.
Comparative example 1
1mol of sodium oxalate Na 2 C 2 O 4 Adding into water, stirring to dissolve, and adding 0.4mol of FeCl 2 And 0.6mol of MnCl 2 Ultrasonic stirring to form Fe 0.4 Mn 0.6 C 2 O 4 Precipitating, filtering and washing the precipitate, and collecting the precipitate after vacuum drying for later use.
1mol of lithium dihydrogen phosphate with the grain diameter of 1-2 mu m and 0.98mol of Fe 0.4 Mn 0.6 C 2 O 4 Mixing, then adding 0.02mol of Co (OH) 2 Stirring nanometer powder (20-30nm) and 0.05456mol of glucose in a high-speed stirrer to obtain a mixed material. And (3) performing jet milling on the mixed material, controlling the crushing particle size to reach 300-400nm, collecting the crushed mixed material, stirring the mixed material in a high-speed stirrer at 2000rpm for 1h, and fully and uniformly mixing the materials.
And heating the fully mixed materials to 400 ℃ at the speed of 2 ℃/min under the protection of nitrogen, preserving heat for 4h, then continuously heating to 710 ℃ at the speed of 2 ℃/min, preserving heat for 10h, naturally cooling, and crushing the obtained lithium manganese iron phosphate to D50, sieving the D50 on a screen of 1-2 mu m and a 400-mesh sieve to obtain the lithium manganese iron phosphate material.
Comparative example 2
1mol of sodium oxalate Na 2 C 2 O 4 Adding into water, stirring until the mixture is completely dissolved, and then adding 0.4mol of FeCl 2 And 0.6mol of MnCl 2 Ultrasonic stirring to form Fe 0.4 Mn 0.6 C 2 O 4 Precipitating, filtering and washing the precipitate, drying in vacuum and collecting for later use.
1mol of lithium dihydrogen phosphate with the grain diameter of 1-2 mu m and 0.995mol of Fe 0.4 Mn 0.6 C 2 O 4 Mixing, then adding 0.005mol of Co (OH) 2 Stirring nanometer powder (20-30nm) and 0.02182mol of glucose in a high-speed stirrer to obtain a mixed material. And (3) carrying out jet milling on the mixed material for crushing, wherein the crushing granularity reaches 300-400nm, collecting the crushed mixed material, stirring the mixed material in a high-speed stirrer at 2000rpm for 1h, and fully and uniformly mixing the materials.
And heating the fully mixed materials to 400 ℃ at a speed of 2 ℃/min under the protection of nitrogen, preserving heat for 4h, continuously heating to 710 ℃ at a speed of 2 ℃/min, preserving heat for 10h, naturally cooling, and crushing the obtained lithium manganese iron phosphate after calcination until the powder D50 is screened on a 400-mesh screen with the size of 1-2 mu m to obtain the lithium manganese iron phosphate material.
Comparative example 3
1mol of sodium oxalate Na 2 C 2 O 4 Adding 3.5L of water, stirring until the mixture is completely dissolved, and then adding 0.3mol of FeCl 2 And 0.7mol of MnCl 2 The mixture is fully and evenly mixed by ultrasonic stirring to form Fe 0.3 Mn 0.7 C 2 O 4 Precipitating, collecting precipitate, filtering, washing, and vacuum drying.
Taking 1mol of lithium dihydrogen phosphate with the particle diameter of 1-2 μm and 0.96mol of the above Fe 0.4 Mn 0.6 C 2 O 4 The precipitates were mixed and then 0.04mol of Co (OH) was added 2 And (3) fully stirring the nano powder (with the particle size of 20-30nm) and 0.03817mol of glucose in a high-speed stirrer to obtain a mixed material. Pulverizing the above mixed material with jet mill, controlling the pulverizing particle size to 300-Stirring at medium 2000rpm for 1h, and mixing the materials thoroughly.
And heating the fully mixed materials to 400 ℃ at the speed of 2 ℃/min under the protection of nitrogen, preserving heat for 4h, then continuously heating to 670 ℃ at the speed of 2 ℃/min, preserving heat for 10h, then naturally cooling, and crushing the obtained lithium manganese iron phosphate to D50, sieving the D50 on a 1-2 mu m sieve of 400 meshes, thereby obtaining the lithium manganese iron phosphate material.
Examples of the experiments
The lithium iron manganese phosphate materials prepared in the above examples 1-3 and comparative examples 1-2 were used to manufacture and test lithium iron manganese phosphate button cells. The step of electrochemical performance testing comprises:
(1) assembling the lithium iron manganese phosphate button battery: lithium manganese iron phosphate: SP: PVDF 90: 5: 5 homogenizing, coating on aluminum foil with thickness of 20 μm, and making into positive plate with surface density of 8mg/cm 2 . And (3) carrying out buckling and electricity assembly by using the button battery case made of R2032, and dropwise adding 80 mu mL of electrolyte by adopting a PE (polyethylene) diaphragm.
(2) Physical and chemical testing of materials: the carbon content was measured using an infrared carbon sulfur instrument, the element doping amount was measured using an ICP-OES tester, the particle size was measured using a laser particle size analyzer, and the results of the physicochemical measurements are shown in table 1.
(3) 1C cycle performance testing was performed at 25 ℃: the lithium iron manganese phosphate button cells in the examples and the comparative examples are tested by using a blue tester, the prepared button cell is placed in a high-temperature oven at 25 ℃ for charge and discharge tests, the voltage range is 2.0V-4.35V, 0.1C is charged and discharged for activation for one circle, then 0.5C constant current and constant voltage charging is carried out, the cutoff current is 0.05C, 1C current is used for constant current discharging, 100 circles are circulated, relevant data of parameters such as the first discharge capacity, the first coulombic efficiency, the 100 th circle discharge capacity and the 100 th circle capacity retention rate are obtained, and the test results are shown in Table 2.
Table 1 lithium manganese iron phosphate each parameter test results
TABLE 2 test of the cycle performance of lithium iron manganese phosphate material at 25 deg.C
As can be seen from the data in the above table 1-2, in the scheme in the embodiments 1-3 of the present application, the carbon content, the element doping amount, and the particle size of the material satisfy the condition that 0.5 ≤ 100 × bz/(a + b) ≤ 1.3, and the particle size, the carbon content, and the element doping amount have a better matching degree, so that ions and electrons in the material have a better migration path, the capacity of the lithium manganese iron phosphate material can be well exerted, the electrical property of the positive electrode material is better, and the material structure is stable, so that the cycle stability of the material is ensured.
In the schemes of the comparative examples 1 and 2, the carbon content, the element doping amount and the granularity do not meet the set matching degree, the carbon content, the element doping amount and the granularity of the material do not reach the optimal matching degree, the synergistic effect of the carbon content, the element doping amount and the granularity is weak, and the specific capacity and the cycling stability of the material are reduced.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (10)
1. The high-performance lithium iron manganese phosphate cathode material is characterized by comprising LiMn x Fe y M z PO 4 The chemical structure shown;
wherein, the M element is at least one of Cr, Ti, Mg, Ni, Co, Cu, Zn and the like;
the parameters satisfy the following relations: x + y + z is equal to 1, x is more than or equal to 0.5 and less than or equal to 0.8, z is more than or equal to 0.005 and less than or equal to 0.02, a is more than or equal to 0.05 and less than or equal to 0.5, and b is more than or equal to 1 and less than or equal to 2.5;
the primary particle size D50 value a of the positive electrode material is 0.05-0.5 mu m, and the carbon content value b is 1-2.5 wt%.
2. The high-performance lithium iron manganese phosphate cathode material according to claim 1, wherein the element doping amount z, the primary particle size D50 value a and the carbon content value b of the cathode material satisfy the following relationships: 0.5 is less than or equal to 100 xbz/(a + b) is less than or equal to 1.3.
3. The method for preparing the high-performance lithium iron manganese phosphate positive electrode material of claim 1 or 2, which is characterized by comprising the following steps of:
(1) dissolving soluble oxalate in water, and adding soluble Fe 2+ Salt and soluble Mn 2+ Salt, reacting to form FeMnC 2 O 4 Precipitating and collecting precipitate;
(2) taking lithium dihydrogen phosphate LiH 2 PO 4 And said FeMnC 2 O 4 Precipitating and mixing, and adding a doping compound and a carbon source material according to the selected doping elements for mixing to obtain a mixed material;
(3) and calcining the obtained mixed material in a protective atmosphere to obtain the catalyst.
4. The method for preparing the high-performance lithium iron manganese phosphate cathode material according to claim 3, wherein in the step (1), the soluble oxalate and the soluble Fe are used 2+ Salt and soluble Mn 2+ The molar ratio of the salt is 1: x: 1-x, wherein x is 0.2-0.5;
preferably, the soluble oxalate salt comprises sodium oxalate, Na 2 C 2 O 4 、K 2 C 2 O 4 Or (NH) 4 ) 2 C 2 O 4 ；
Preferably, the soluble Fe 2+ The salt comprising FeCl 2 Or FeSO 4 ；
Preferably, the soluble Mn is 2+ The salt comprises MnCl 2 Or MnSO 4 。
5. The preparation method of the high-performance lithium iron manganese phosphate cathode material according to claim 3 or 4, wherein in the step (2), the lithium dihydrogen phosphate LiHPO 4 、FeMnC 2 O 4 The mol ratio of M to carbon source materials in the precipitation and doping compounds is 1: (1-z): z: 0.021-0.055, wherein z is 0.005-0.02;
preferably, the doping compound comprises an oxide and/or hydroxide of a doping element;
preferably, the carbon source material includes a saccharide, and more preferably, the carbon source material includes glucose, sucrose or starch.
6. The preparation method of the high-performance lithium iron manganese phosphate positive electrode material according to any one of claims 3 to 5, wherein in the step (2):
the lithium dihydrogen phosphate LiH 2 PO 4 The particle diameter of (A) is 1-2 μm;
the particle size of the doping compound is 20-30 nm.
7. The method for preparing the high-performance lithium iron manganese phosphate cathode material as claimed in any one of claims 3 to 6, wherein the step (2) further comprises the step of pulverizing the obtained mixed material to a particle size of 300-400 nm.
8. The method for preparing the high-performance lithium iron manganese phosphate cathode material as claimed in any one of claims 3 to 7, wherein the temperature of the calcination step in the step (3) is 350-700 ℃;
preferably, the calcining step comprises: heating to 350-400 ℃ at the speed of 1-3 ℃/min for heat preservation for 3-5h, and continuing heating to 600-700 ℃ at the speed of 1-3 ℃/min for heat preservation for 10-15 h.
9. Use of the lithium iron manganese phosphate positive electrode material according to claim 1 or 2 or the lithium iron manganese phosphate positive electrode material prepared by the method according to any one of claims 3 to 8 for preparing a lithium ion battery positive electrode or a lithium ion battery.
10. A lithium ion battery anode or a lithium ion battery prepared from the lithium iron manganese phosphate anode material of claim 1 or 2 or the lithium iron manganese phosphate anode material prepared by the method of any one of claims 3 to 8.
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