CN107039648A - The preparation method of the composite ferric lithium phosphate material of the order mesoporous carbon coating of N doping - Google Patents
The preparation method of the composite ferric lithium phosphate material of the order mesoporous carbon coating of N doping Download PDFInfo
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- CN107039648A CN107039648A CN201710396481.6A CN201710396481A CN107039648A CN 107039648 A CN107039648 A CN 107039648A CN 201710396481 A CN201710396481 A CN 201710396481A CN 107039648 A CN107039648 A CN 107039648A
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- doping
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- mesoporous carbon
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- 239000000463 material Substances 0.000 title claims abstract description 82
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 238000000576 coating method Methods 0.000 title claims abstract description 52
- 239000011248 coating agent Substances 0.000 title claims abstract description 51
- 239000002131 composite material Substances 0.000 title claims abstract description 51
- 229910001386 lithium phosphate Inorganic materials 0.000 title claims abstract description 46
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 52
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 42
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 40
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 34
- 239000008367 deionised water Substances 0.000 claims abstract description 33
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 33
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 30
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 24
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 18
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 16
- 239000011574 phosphorus Substances 0.000 claims abstract description 16
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 15
- 238000001914 filtration Methods 0.000 claims abstract description 15
- 229910052742 iron Inorganic materials 0.000 claims abstract description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000001816 cooling Methods 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 11
- 235000019441 ethanol Nutrition 0.000 claims abstract description 8
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims description 106
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 39
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 13
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 11
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 11
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 10
- 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 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- 239000008103 glucose Substances 0.000 claims description 9
- 238000005303 weighing Methods 0.000 claims description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 claims description 6
- 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 5
- 229930006000 Sucrose Natural products 0.000 claims description 5
- 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 5
- 239000005720 sucrose Substances 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 3
- 229920000877 Melamine resin Polymers 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- MCDLETWIOVSGJT-UHFFFAOYSA-N acetic acid;iron Chemical compound [Fe].CC(O)=O.CC(O)=O MCDLETWIOVSGJT-UHFFFAOYSA-N 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 3
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 3
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 3
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 3
- 239000011790 ferrous sulphate Substances 0.000 claims description 3
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 3
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 3
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 3
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 3
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 3
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 3
- 229920000128 polypyrrole Polymers 0.000 claims description 3
- 230000001476 alcoholic effect Effects 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 claims 1
- 238000003756 stirring Methods 0.000 abstract 2
- 230000015572 biosynthetic process Effects 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- 229910052493 LiFePO4 Inorganic materials 0.000 description 6
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 6
- 239000011148 porous material Substances 0.000 description 5
- 238000001354 calcination Methods 0.000 description 4
- 238000002242 deionisation method Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-L Phosphate ion(2-) Chemical compound OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 description 2
- QSNQXZYQEIKDPU-UHFFFAOYSA-N [Li].[Fe] Chemical compound [Li].[Fe] QSNQXZYQEIKDPU-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 2
- 235000019289 ammonium phosphates Nutrition 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000005253 cladding Methods 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000010450 olivine Substances 0.000 description 1
- 229910052609 olivine Inorganic materials 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
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- 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
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
-
- 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
-
- 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)
- Composite Materials (AREA)
- Engineering & Computer Science (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
A kind of preparation method of the composite ferric lithium phosphate material of the order mesoporous carbon coating of N doping, comprises the following steps：Step one：Weigh carbon source to be dissolved in deionized water, add nitrogen source stirring, cool down and take out after first the first preset time of preset temperature hydro-thermal reaction, after being washed with deionized water and absolute ethyl alcohol, the second preset time is dried in the second preset temperature；Step 2：N doping persursor material is dissolved in deionized water with potassium hydroxide; it is put in the stirring of the 3rd preset temperature in container and dries the 3rd preset time; again under nitrogen protection, and after the 4th preset temperature calcines the 4th preset time cool down, with deionized water and washes of absolute alcohol, filtering and drying；Step 3：Weigh N doping ordered mesoporous carbon material and add the progress preset time of ultrasonic disperse the 5th in ethanol solution, add source of iron, lithium source and phosphorus source and carry out the preset time of ultrasonic disperse the 6th, the 7th preset time is reacted in the 5th preset temperature, is heat-treated under a nitrogen after cooling taking-up is scrubbed and dry.
Description
【Technical field】
The present invention relates to the phosphoric acid of cell positive material technical field, more particularly to a kind of order mesoporous carbon coating of N doping
The preparation method of iron lithium composite material.
【Background technology】
The diffusion of the electronic conductance and lithium ion of lithium iron phosphate positive material has become restriction lithium iron phosphate positive material
The key issue of application.Existing technical method is used as carbon source coated LiFePO 4 for lithium ion batteries positive pole material usually using sucrose, glucose etc.
Material, improves the electronic conductance of lithium iron phosphate positive material.But the control to lithium iron phosphate particles size such as sucrose, glucose
And have limitation to the transmission of electronics and ion, lithium iron phosphate positive material structure is easily caused under the conditions of big multiplying power discharging and is collapsed
Collapse, and then cause the lithium battery cycle life for using the lithium iron phosphate positive material to prepare short.Because of the particle of LiFePO 4 material
Particle diameter, microscopic appearance, crystal structure, doping and the species and the factor such as content that coat material, it is difficult to pass through single improvement
Method reaches ideal effect, when such as carbon coating improves LiFePO4, and homogeneous, the complete carbon coating layer of acquisition is relatively difficult, and contains
Carbon amounts is relatively low, and resistivity is higher, and the electron conduction effect of material is undesirable.
In consideration of it, real be necessary to provide a kind of composite ferric lithium phosphate material of the order mesoporous carbon coating of new N doping
Preparation method overcomes disadvantages described above.
【The content of the invention】
It is an object of the invention to provide a kind of preparation side of the composite ferric lithium phosphate material of the order mesoporous carbon coating of N doping
Method, the composite ferric lithium phosphate material of the order mesoporous carbon coating of N doping prepared using the inventive method is uniformly dispersed, energy of adsorption
Power is strong, and hole is more, and aperture is small, and specific surface area can improve greatly the conducting power of electronic and ionic, so that orderly using N doping
The capacity for the lithium battery that the composite ferric lithium phosphate material of mesoporous carbon coating is further prepared as positive electrode is high and charge and discharge is electrical
Can be excellent.
To achieve these goals, the present invention provides a kind of composite ferric lithium phosphate material of the order mesoporous carbon coating of N doping
Preparation method, comprise the following steps：
Step one：The carbon source for first weighing the 20%-40% for the mass ratio for accounting for ionized water is dissolved in deionized water and forms
One mixture, then add account for the first mixture quality than 3.5%-7.1% nitrogen source be dissolved in the first mixture and being stirred
Mix to form the second mixture, then the second mixture is cooled to room under the first preset temperature after the preset time of hydro-thermal reaction first
Take out, after finally the second mixture is washed with deionized water and absolute ethyl alcohol successively, dried under the second preset temperature after temperature
Second preset time, is made N doping persursor material.
Step 2：First by obtained N doping persursor material in step one and potassium hydroxide in mass ratio 1：3-5 ratio
Example is dissolved in deionized water the 3rd mixture of formation, wherein, the gross mass of N doping persursor material and potassium hydroxide and go from
The mass ratio of sub- water is 1：20-30, is put in container after then the 3rd mixture is stirred under the 3rd preset temperature and does
The 4th mixture is formed after dry 3rd preset time, then, and under the 4th preset temperature by the 4th mixture under nitrogen protection
Calcine to take out after cooling down after the 4th preset time and obtain the 5th mixture, the 5th mixture is finally used into deionized water and nothing successively
After water-ethanol cleaning, filtering and drying, N doping ordered mesoporous carbon material is made.
Step 3：The N doping ordered mesoporous carbon material for first weighing the 6%-8% for accounting for source of iron, lithium source and phosphorus source gross mass adds
Enter and carry out forming the 6th mixture after the preset time of ultrasonic disperse the 5th in ethanol solution, then added again in the 6th mixture
Source of iron, lithium source and phosphorus source are carried out after the preset time of ultrasonic disperse the 6th, then the 7th preset time of reaction under the 5th preset temperature
The 7th mixture is formed afterwards, and finally cooling is taken out at the 7th mixture under nitrogen protection heat after filtering, washing and dry
Reason, is made the composite ferric lithium phosphate material of the order mesoporous carbon coating of N doping.
Specifically, the first preset temperature described in step one is：200℃-260℃；First preset time is：4h-6h；
Second preset temperature is：50℃-70℃；Second preset time is：24h-48h.
Specifically, the 3rd preset temperature described in step 2 is：60℃-80℃；3rd preset time is：24h-48h；
4th preset temperature：600℃-750℃；4th preset time：2h-3h.
Specifically, the 5th preset time described in step 3 is：30min-60min；6th preset time is：1h-2h；
5th preset temperature is：180℃-200℃；7th preset time is：12h-18h；The temperature of heat treatment is：650 DEG C -750 DEG C,
The time of heat treatment is：5h-8h.
Specifically, the mol ratio of the source of iron, lithium source, phosphorus source is 1-1.5：2-4：1.05-1.1.
Specifically, described source of iron can be any one in frerrous chloride, ferrous sulfate, ferrous nitrate and ferrous acetate
Kind；Described lithium source can be any one in lithium hydroxide and lithium carbonate；Described phosphorus source can be phosphoric acid, biphosphate
Any one in ammonium and diammonium hydrogen phosphate.
Specifically, the carbon source can be any one in glucose, sucrose and citric acid.
Specifically, the nitrogen source can be any in acetamide, benzene methanamine, melamine, polyacrylonitrile and polypyrrole
It is a kind of.
Compared with prior art, the composite ferric lithium phosphate material for the order mesoporous carbon coating of a kind of N doping that the present invention is provided
Preparation method, the composite ferric lithium phosphate material of the order mesoporous carbon coating of N doping prepared using the inventive method is scattered equal
Even, high adsorption capacity, hole is more, and aperture is small, and specific surface area can improve greatly the conducting power of electronic and ionic, so that using nitrogen
The capacity of lithium battery that the composite ferric lithium phosphate material of doping ordered mesopore carbon cladding is further prepared as positive electrode it is high and
Charge-discharge performance is excellent.
【Brief description of the drawings】
Fig. 1 is the SEM of the composite ferric lithium phosphate material of the order mesoporous carbon coating of N doping prepared by the embodiment of the present invention 2
Figure.
Fig. 2 is the composite ferric lithium phosphate material of the order mesoporous carbon coating of N doping prepared by the embodiment of the present invention 1,2,3 and 4
Adsorption/desorption isotherms figure.
Fig. 3 is the composite ferric lithium phosphate material of the order mesoporous carbon coating of N doping prepared by the embodiment of the present invention 1,2,3 and 4
Graph of pore diameter distribution.
Fig. 4 is the composite ferric lithium phosphate material of the order mesoporous carbon coating of N doping prepared by the embodiment of the present invention 1,2,3 and 4
The charge graph of the lithium battery further prepared as positive electrode.
Fig. 5 is the composite ferric lithium phosphate material of the order mesoporous carbon coating of N doping prepared by the embodiment of the present invention 1,2,3 and 4
The discharge curve of the lithium battery further prepared as positive electrode.
Fig. 6 is the XRD of the composite ferric lithium phosphate material of the order mesoporous carbon coating of N doping prepared by the embodiment of the present invention 2
Spectrum.
【Embodiment】
In order that the purpose of the present invention, technical scheme and advantageous effects become apparent from understanding, below in conjunction with accompanying drawing and
Embodiment, the present invention will be described in further detail.It should be appreciated that the specific implementation described in this specification
Mode is not intended to limit the present invention just for the sake of explaining the present invention.
The present invention provides a kind of preparation method of the composite ferric lithium phosphate material of the order mesoporous carbon coating of N doping, including such as
Lower step：
Step one：The carbon source for first weighing the 20%-40% for the mass ratio for accounting for ionized water is dissolved in deionized water and forms
One mixture, then add account for the first mixture quality than 3.5%-7.1% nitrogen source be dissolved in the first mixture and being stirred
Mix to form the second mixture, then the second mixture is cooled to room under the first preset temperature after the preset time of hydro-thermal reaction first
Take out, after finally the second mixture is washed with deionized water and absolute ethyl alcohol successively, dried under the second preset temperature after temperature
Second preset time, is made N doping persursor material.
Step 2：First by obtained N doping persursor material in step one and potassium hydroxide in mass ratio 1：3-5 ratio
Example is dissolved in deionized water the 3rd mixture of formation, wherein, the gross mass of N doping persursor material and potassium hydroxide and go from
The mass ratio of sub- water is 1：20-30, is put in container after then the 3rd mixture is stirred under the 3rd preset temperature and does
The 4th mixture is formed after dry 3rd preset time, then, and under the 4th preset temperature by the 4th mixture under nitrogen protection
Calcine to take out after cooling down after the 4th preset time and obtain the 5th mixture, the 5th mixture is finally used into deionized water and nothing successively
After water-ethanol cleaning, filtering and drying, N doping ordered mesoporous carbon material is made.
Step 3：The N doping ordered mesoporous carbon material for first weighing the 6%-8% for accounting for source of iron, lithium source and phosphorus source gross mass adds
Enter and carry out forming the 6th mixture after the preset time of ultrasonic disperse the 5th in ethanol solution, then added again in the 6th mixture
Source of iron, lithium source and phosphorus source are carried out after the preset time of ultrasonic disperse the 6th, then the 7th preset time of reaction under the 5th preset temperature
The 7th mixture is formed afterwards, and finally cooling is taken out at the 7th mixture under nitrogen protection heat after filtering, washing and dry
Reason, is made the composite ferric lithium phosphate material of the order mesoporous carbon coating of N doping.
Specifically, the first preset temperature described in step one is：200℃-260℃；First preset time is：4h-6h；
Second preset temperature is：50℃-70℃；Second preset time is：24h-48h.
Specifically, the 3rd preset temperature described in step 2 is：60℃-80℃；3rd preset time is：24h-48h；
4th preset temperature：600℃-750℃；4th preset time：2h-3h.
Specifically, the 5th preset time described in step 3 is：30min-60min；6th preset time is：1h-2h；
5th preset temperature is：180℃-200℃；7th preset time is：12h-18h；The temperature of heat treatment is：650 DEG C -750 DEG C,
The time of heat treatment is：5h-8h.
Specifically, the mol ratio of the source of iron, lithium source, phosphorus source is 1-1.5：2-4：1.05-1.1.
Specifically, described source of iron can be any one in frerrous chloride, ferrous sulfate, ferrous nitrate and ferrous acetate
Kind；Described lithium source can be any one in lithium hydroxide and lithium carbonate；Described phosphorus source can be phosphoric acid, biphosphate
Any one in ammonium and diammonium hydrogen phosphate.
Specifically, the carbon source can be any one in glucose, sucrose and citric acid.
Specifically, the nitrogen source can be any in acetamide, benzene methanamine, melamine, polyacrylonitrile and polypyrrole
It is a kind of.
Embodiment：
Embodiment 1：
Step one：The glucose for first weighing 16.0g is dissolved in 40.0g deionized water and forms the first mixture, then
Addition 3.96g acetamide, which is dissolved in the first mixture, to be stirred to form the second mixture, then by the second mixture at 220 DEG C
It is cooled to after room temperature and takes out after lower hydro-thermal reaction 5h, finally washs the second mixture with deionized water and absolute ethyl alcohol successively
Afterwards, 24h is dried at 50 DEG C, N doping persursor material is made.
Step 2：First by obtained N doping persursor material in step one and potassium hydroxide in mass ratio 1：3 ratio
The 3rd mixture of formation in deionized water is dissolved in, wherein, the gross mass and deionization of N doping persursor material and potassium hydroxide
The mass ratio of water is 1：20, it is put in dry in container after then the 3rd mixture is stirred at 60 DEG C the is formed after 24h
Four mixtures, then, and taking-up obtains the 5th mixing after cooling after calcining 2h at 600 DEG C. by the 4th mixture under nitrogen protection
Thing, finally by the 5th mixture successively with after deionized water and washes of absolute alcohol, filtering and drying, obtained N doping is situated between in order
Hole carbon material.
Step 3：First weigh and account for 6% N doping of frerrous chloride, lithium hydroxide and ammonium dihydrogen phosphate gross mass and be situated between in order
Hole carbon material, which is added in ethanol solution, to carry out forming the 6th mixture after ultrasonic disperse 30min, then again in the 6th mixture
Add frerrous chloride, lithium hydroxide and ammonium dihydrogen phosphate to carry out after ultrasonic disperse 1h, then react at 180 DEG C the is formed after 12h
Seven mixtures, wherein, frerrous chloride, lithium hydroxide, the mol ratio of ammonium dihydrogen phosphate are 1：2：1.05, finally cooling, which is taken out, to be passed through
The 7th mixture is heat-treated under nitrogen protection after filtering, wash and drying, wherein the temperature being heat-treated is 650 DEG C, heat treatment
Time be 5h, the composite ferric lithium phosphate material of N doping order mesoporous carbon coating is made.
Embodiment 2：
Step one：The glucose for first weighing 16.0g is dissolved in 40.0g deionized water and forms the first mixture, then
Addition 3.3g acetamide, which is dissolved in the first mixture, to be stirred to form the second mixture, then by the second mixture at 220 DEG C
It is cooled to after room temperature and takes out after lower hydro-thermal reaction 5h, finally washs the second mixture with deionized water and absolute ethyl alcohol successively
Afterwards, 24h is dried at 50 DEG C, N doping persursor material is made.
Step 2：First by obtained N doping persursor material in step one and potassium hydroxide in mass ratio 1：3 ratio
The 3rd mixture of formation in deionized water is dissolved in, wherein, the gross mass and deionization of N doping persursor material and potassium hydroxide
The mass ratio of water is 1：20, it is put in dry in container after then the 3rd mixture is stirred at 60 DEG C the is formed after 24h
Four mixtures, then, and taking-up obtains the 5th mixing after cooling after calcining 2h at 600 DEG C. by the 4th mixture under nitrogen protection
Thing, finally by the 5th mixture successively with after deionized water and washes of absolute alcohol, filtering and drying, obtained N doping is situated between in order
Hole carbon material.
Step 3：First weigh and account for 6% N doping of frerrous chloride, lithium hydroxide and ammonium dihydrogen phosphate gross mass and be situated between in order
Hole carbon material, which is added in ethanol solution, to carry out forming the 6th mixture after ultrasonic disperse 30min, then again in the 6th mixture
Add frerrous chloride, lithium hydroxide and ammonium dihydrogen phosphate to carry out after ultrasonic disperse 1h, then react at 180 DEG C the is formed after 12h
Seven mixtures, wherein, frerrous chloride, lithium hydroxide, the mol ratio of ammonium dihydrogen phosphate are 1：2：1.05, finally cooling, which is taken out, to be passed through
The 7th mixture is heat-treated under nitrogen protection after filtering, wash and drying, wherein the temperature being heat-treated is 650 DEG C, heat treatment
Time be 5h, the composite ferric lithium phosphate material of N doping order mesoporous carbon coating is made.
Embodiment 3：
Step one：The glucose for first weighing 16.0g is dissolved in 40.0g deionized water and forms the first mixture, then
Addition 2.64g acetamide, which is dissolved in the first mixture, to be stirred to form the second mixture, then by the second mixture at 220 DEG C
It is cooled to after room temperature and takes out after lower hydro-thermal reaction 5h, finally washs the second mixture with deionized water and absolute ethyl alcohol successively
Afterwards, 24h is dried at 50 DEG C, N doping persursor material is made.
Step 2：First by obtained N doping persursor material in step one and potassium hydroxide in mass ratio 1：3 ratio
The 3rd mixture of formation in deionized water is dissolved in, wherein, the gross mass and deionization of N doping persursor material and potassium hydroxide
The mass ratio of water is 1：20, it is put in dry in container after then the 3rd mixture is stirred at 60 DEG C the is formed after 24h
Four mixtures, then, and taking-up obtains the 5th mixing after cooling after calcining 2h at 600 DEG C. by the 4th mixture under nitrogen protection
Thing, finally by the 5th mixture successively with after deionized water and washes of absolute alcohol, filtering and drying, obtained N doping is situated between in order
Hole carbon material.
Step 3：First weigh and account for 6% N doping of frerrous chloride, lithium hydroxide and ammonium dihydrogen phosphate gross mass and be situated between in order
Hole carbon material, which is added in ethanol solution, to carry out forming the 6th mixture after ultrasonic disperse 30min, then again in the 6th mixture
Add source of iron, lithium source and phosphorus source to carry out after ultrasonic disperse 1h, then the 7th mixture of formation after 12h is reacted at 180 DEG C, wherein,
Frerrous chloride, lithium hydroxide, the mol ratio of ammonium dihydrogen phosphate are 1：2：1.05, finally cooling is taken out through filtering, washing and dried
The 7th mixture is heat-treated under nitrogen protection afterwards, wherein the temperature being heat-treated is 650 DEG C, the time of heat treatment is 5h, system
Obtain the composite ferric lithium phosphate material of the order mesoporous carbon coating of N doping.
Embodiment 4：
Step one：The glucose for first weighing 16.0g is dissolved in 40.0g deionized water and forms the first mixture, then
Addition 1.98g acetamide, which is dissolved in the first mixture, to be stirred to form the second mixture, then by the second mixture at 220 DEG C
It is cooled to after room temperature and takes out after lower hydro-thermal reaction 5h, finally washs the second mixture with deionized water and absolute ethyl alcohol successively
Afterwards, 24h is dried at 50 DEG C, N doping persursor material is made.
Step 2：First by obtained N doping persursor material in step one and potassium hydroxide in mass ratio 1：3 ratio
The 3rd mixture of formation in deionized water is dissolved in, wherein, the gross mass and deionization of N doping persursor material and potassium hydroxide
The mass ratio of water is 1：20, it is put in dry in container after then the 3rd mixture is stirred at 60 DEG C the is formed after 24h
Four mixtures, then, and taking-up obtains the 5th mixing after cooling after calcining 2h at 600 DEG C. by the 4th mixture under nitrogen protection
Thing, finally by the 5th mixture successively with after deionized water and washes of absolute alcohol, filtering and drying, obtained N doping is situated between in order
Hole carbon material.
Step 3：First weigh and account for 6% N doping of frerrous chloride, lithium hydroxide and ammonium dihydrogen phosphate gross mass and be situated between in order
Hole carbon material, which is added in ethanol solution, to carry out forming the 6th mixture after ultrasonic disperse 30min, then again in the 6th mixture
Add source of iron, lithium source and phosphorus source to carry out after ultrasonic disperse 1h, then the 7th mixture of formation after 12h is reacted at 180 DEG C, wherein,
Frerrous chloride, lithium hydroxide, the mol ratio of ammonium dihydrogen phosphate are 1：2：1.05, finally cooling is taken out through filtering, washing and dried
The 7th mixture is heat-treated under nitrogen protection afterwards, wherein the temperature being heat-treated is 650 DEG C, the time of heat treatment is 5h, system
Obtain the composite ferric lithium phosphate material of the order mesoporous carbon coating of N doping.
The performance of the composite ferric lithium phosphate material of the order mesoporous carbon coating of N doping prepared using the inventive method is as follows
Table 1, wherein, the composite ferric lithium phosphate material of the order mesoporous carbon coating of N doping made from embodiment 1 is sample A；Embodiment 2 is made
The composite ferric lithium phosphate material of the order mesoporous carbon coating of N doping obtained is sample B；N doping made from embodiment 3 is order mesoporous
The composite ferric lithium phosphate material of carbon coating is sample C；The LiFePO4 of the order mesoporous carbon coating of N doping made from embodiment 4 is answered
Condensation material is sample D.
Table 1：
As shown in Table 1, show that nitrogen content is different, the ratio table of the composite ferric lithium phosphate material of the order mesoporous carbon coating of N doping
Area difference is larger, therefore suitable carbon-nitrogen ratio is to improve the composite ferric lithium phosphate material electrification of the order mesoporous carbon coating of N doping
Learn the premise of performance.Simultaneously, it can be seen that sample B specific surface area is maximum, and specific surface area is 880.437m2/ g, average pore size
Minimum, absorption average pore size is 1.526nm, and sample B specific surface area, absorption average pore size parameter is optimal.
Fig. 1 is the SEM of the composite ferric lithium phosphate material of the order mesoporous carbon coating of N doping prepared by the embodiment of the present invention 2
Figure.Fig. 2 is the suction of the composite ferric lithium phosphate material of the order mesoporous carbon coating of N doping prepared by the embodiment of the present invention 1,2,3 and 4
Attached desorption isotherm figure.Fig. 3 is the LiFePO4 of the order mesoporous carbon coating of N doping prepared by the embodiment of the present invention 1,2,3 and 4
The graph of pore diameter distribution of composite.Fig. 4 is the phosphorus of the order mesoporous carbon coating of N doping prepared by the embodiment of the present invention 1,2,3 and 4
The charge graph for the lithium battery that sour iron lithium composite material is further prepared as positive electrode.Fig. 5 be the embodiment of the present invention 1,
2nd, the lithium that the composite ferric lithium phosphate material of the 3 and 4 order mesoporous carbon coatings of N doping prepared is further prepared as positive electrode
The discharge curve of battery.Fig. 6 is the LiFePO4 composite wood of the order mesoporous carbon coating of N doping prepared by the embodiment of the present invention 2
The XRD spectrum of material.
From Fig. 1 to Fig. 6, the LiFePO4 of the order mesoporous carbon coating of N doping prepared using the embodiment of the present invention 2
Composite is olivine crystal formation, and principal phase crystal structure is without obvious change；The LiFePO4 of the order mesoporous carbon coating of N doping is answered
The hole of condensation material is more, adds contact point position, improves electronics conduction velocity；Aperture is smaller, and specific surface area is bigger, uses nitrogen
The capacity for the lithium battery that the composite ferric lithium phosphate material of doping ordered mesopore carbon cladding is further prepared as positive electrode is got over
It is high.
In summary, the present invention provides a kind of preparation side of the composite ferric lithium phosphate material of the order mesoporous carbon coating of N doping
Method, the composite ferric lithium phosphate material of the order mesoporous carbon coating of N doping prepared using the inventive method is uniformly dispersed, energy of adsorption
Power is strong, and hole is more, and aperture is small, and specific surface area can improve greatly the conducting power of electronic and ionic, so that orderly using N doping
The capacity for the lithium battery that the composite ferric lithium phosphate material of mesoporous carbon coating is further prepared as positive electrode is high and charge and discharge is electrical
Can be excellent.
The present invention is not restricted to described in specification and embodiment, therefore for the personnel of familiar field
Additional advantage and modification is easily achieved, therefore in the essence of the universal limited without departing substantially from claim and equivalency range
In the case of refreshing and scope, the present invention is not limited to specific details, representational equipment and shown here as the diagram with description
Example.
Claims (8)
1. a kind of preparation method of the composite ferric lithium phosphate material of the order mesoporous carbon coating of N doping, it is characterised in that including such as
Lower step：
Step one：First weigh the 20%-40% for the mass ratio for accounting for ionized water carbon source be dissolved in deionized water formed first mix
Compound, then add account for the first mixture quality than 3.5%-7.1% nitrogen source be dissolved in the first mixture and be stirred shape
Into the second mixture, then after second mixture is cooled into room temperature after the preset time of hydro-thermal reaction first under the first preset temperature
Take out, after finally the second mixture is washed with deionized water and absolute ethyl alcohol successively, second is dried under the second preset temperature
Preset time, is made N doping persursor material；
Step 2：First by obtained N doping persursor material in step one and potassium hydroxide in mass ratio 1：3-5 ratio is molten
The 3rd mixture is formed in deionized water, wherein, the gross mass and deionized water of N doping persursor material and potassium hydroxide
Mass ratio be 1：20-30, is put in container after then the 3rd mixture is stirred under the 3rd preset temperature and dries the
The 4th mixture is formed after three preset times, then, and calcined under the 4th preset temperature by the 4th mixture under nitrogen protection
Taken out after being cooled down after 4th preset time and obtain the 5th mixture, the 5th mixture is finally used into deionized water and anhydrous second successively
After alcohol cleaning, filtering and drying, N doping ordered mesoporous carbon material is made；
Step 3：The N doping ordered mesoporous carbon material for first weighing the 6%-8% for accounting for source of iron, lithium source and phosphorus source gross mass adds second
Carry out forming the 6th mixture after the preset time of ultrasonic disperse the 5th in alcoholic solution, then add iron in the 6th mixture again
Source, lithium source and phosphorus source are carried out after the preset time of ultrasonic disperse the 6th, then are reacted under the 5th preset temperature after the 7th preset time
The 7th mixture is formed, finally cooling is taken out through filtering, washing and is heat-treated the 7th mixture under nitrogen protection after drying,
The composite ferric lithium phosphate material of the order mesoporous carbon coating of N doping is made.
2. the preparation method of the composite ferric lithium phosphate material of the order mesoporous carbon coating of N doping according to claim 1, its
It is characterised by：The first preset temperature described in step one is：200℃-260℃；First preset time is：4h-6h；Second is pre-
If temperature is：50℃-70℃；Second preset time is：24h-48h.
3. the preparation method of the composite ferric lithium phosphate material of the order mesoporous carbon coating of N doping according to claim 1, its
It is characterised by：The 3rd preset temperature described in step 2 is：60℃-80℃；3rd preset time is：24h-48h；4th is pre-
If temperature：600℃-750℃；4th preset time：2h-3h.
4. the preparation method of the composite ferric lithium phosphate material of the order mesoporous carbon coating of N doping according to claim 1, its
It is characterised by：The 5th preset time described in step 3 is：30min-60min；6th preset time is：1h-2h；5th is pre-
If temperature is：180℃-200℃；7th preset time is：12h-18h；The temperature of heat treatment is：650 DEG C -750 DEG C, heat treatment
Time be：5h-8h.
5. the preparation method of the composite ferric lithium phosphate material of the order mesoporous carbon coating of N doping according to claim 1, its
It is characterised by：The source of iron, lithium source, the mol ratio of phosphorus source are 1-1.5：2-4：1.05-1.1.
6. the preparation method of the composite ferric lithium phosphate material of the order mesoporous carbon coating of N doping according to claim 5, its
It is characterised by：Described source of iron can be any one in frerrous chloride, ferrous sulfate, ferrous nitrate and ferrous acetate；Institute
The lithium source stated can be any one in lithium hydroxide and lithium carbonate；Described phosphorus source can be phosphoric acid, ammonium dihydrogen phosphate and
Any one in diammonium hydrogen phosphate.
7. the preparation method of the composite ferric lithium phosphate material of the order mesoporous carbon coating of N doping according to claim 1, its
It is characterised by：The carbon source can be any one in glucose, sucrose and citric acid.
8. the preparation method of the composite ferric lithium phosphate material of the order mesoporous carbon coating of N doping according to claim 1, its
It is characterised by：The nitrogen source can be any one in acetamide, benzene methanamine, melamine, polyacrylonitrile and polypyrrole.
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| CN108565446B (en) * | 2018-06-11 | 2021-01-19 | 清华大学深圳研究生院 | Preparation method of porous nitrogen-doped carbon-coated graphite material |
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