CN109599547A - NaTi2(PO4)3-TiO2Preparation method and application of/C composite electrode material - Google Patents
NaTi2(PO4)3-TiO2Preparation method and application of/C composite electrode material Download PDFInfo
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- CN109599547A CN109599547A CN201811497805.6A CN201811497805A CN109599547A CN 109599547 A CN109599547 A CN 109599547A CN 201811497805 A CN201811497805 A CN 201811497805A CN 109599547 A CN109599547 A CN 109599547A
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- 239000007772 electrode material Substances 0.000 title claims abstract description 29
- 239000002131 composite material Substances 0.000 title abstract description 18
- 238000000034 method Methods 0.000 title description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 62
- 239000000463 material Substances 0.000 claims abstract description 30
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000002360 preparation method Methods 0.000 claims abstract description 26
- 239000011734 sodium Substances 0.000 claims abstract description 17
- 238000000498 ball milling Methods 0.000 claims abstract description 14
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 14
- 239000010936 titanium Substances 0.000 claims abstract description 13
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 11
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 11
- 239000002002 slurry Substances 0.000 claims abstract description 9
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000012298 atmosphere Substances 0.000 claims abstract description 8
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 7
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 7
- 239000011574 phosphorus Substances 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims abstract description 7
- 239000006185 dispersion Substances 0.000 claims abstract description 6
- 238000001694 spray drying Methods 0.000 claims abstract 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 37
- 238000005507 spraying Methods 0.000 claims description 10
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 8
- 229910001416 lithium ion Inorganic materials 0.000 claims description 8
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 8
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 8
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 8
- 239000004408 titanium dioxide Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 7
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 7
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 6
- 229910002804 graphite Inorganic materials 0.000 claims description 6
- 239000010439 graphite Substances 0.000 claims description 6
- 229910052744 lithium Inorganic materials 0.000 claims description 6
- BVWCFOXBDSMXEP-UHFFFAOYSA-N 1-(5-acetyl-2-methoxyphenyl)-3-methylbutan-1-one Chemical compound COC1=CC=C(C(C)=O)C=C1C(=O)CC(C)C BVWCFOXBDSMXEP-UHFFFAOYSA-N 0.000 claims description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 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 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 4
- 239000008103 glucose Substances 0.000 claims description 4
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 claims description 4
- 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 3
- 229930006000 Sucrose Natural products 0.000 claims description 3
- 239000002041 carbon nanotube Substances 0.000 claims description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 3
- 239000013078 crystal Substances 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 239000005720 sucrose Substances 0.000 claims description 3
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 229910052786 argon Inorganic materials 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
- 239000001569 carbon dioxide Substances 0.000 claims description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-M dihydrogenphosphate Chemical compound OP(O)([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-M 0.000 claims description 2
- 235000019441 ethanol Nutrition 0.000 claims description 2
- 229910021389 graphene Inorganic materials 0.000 claims description 2
- 229910000402 monopotassium phosphate Inorganic materials 0.000 claims description 2
- 235000019796 monopotassium phosphate Nutrition 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 claims description 2
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- 239000011780 sodium chloride Substances 0.000 claims description 2
- 235000002639 sodium chloride Nutrition 0.000 claims description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 2
- 235000011152 sodium sulphate Nutrition 0.000 claims description 2
- 229910000348 titanium sulfate Inorganic materials 0.000 claims description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 2
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 2
- 239000006245 Carbon black Super-P Substances 0.000 claims 1
- 238000002156 mixing Methods 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000002243 precursor Substances 0.000 abstract 2
- 239000007921 spray Substances 0.000 abstract 2
- 238000005245 sintering Methods 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 13
- 239000012299 nitrogen atmosphere Substances 0.000 description 11
- 239000000126 substance Substances 0.000 description 8
- 229910019441 NaTi2(PO4)3 Inorganic materials 0.000 description 7
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 7
- 230000014759 maintenance of location Effects 0.000 description 7
- 229910001415 sodium ion Inorganic materials 0.000 description 7
- 238000004064 recycling Methods 0.000 description 6
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 6
- 239000006258 conductive agent Substances 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 102220043159 rs587780996 Human genes 0.000 description 5
- 239000011149 active material Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- MJEPCYMIBBLUCJ-UHFFFAOYSA-K sodium titanium(4+) phosphate Chemical compound P(=O)([O-])([O-])[O-].[Ti+4].[Na+] MJEPCYMIBBLUCJ-UHFFFAOYSA-K 0.000 description 3
- 235000010215 titanium dioxide Nutrition 0.000 description 3
- 239000002033 PVDF binder Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 239000002228 NASICON Substances 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000007767 bonding agent Substances 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000003836 solid-state method Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003860 storage 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
- H01M4/362—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
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- 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
-
- 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
Abstract
The invention provides a NaTi2(PO4)3‑TiO2The preparation method of the/C composite electrode material comprises the following steps of (1) mixing a sodium source, a titanium source and a phosphorus source, adding a carbon source and a solvent for ball milling dispersion, and then carrying out spray drying on the slurry after ball milling to obtain a spray precursor; (2) pre-burning the spray precursor in the step (1) in an inert atmosphere at 250-500 ℃ for 2-6 h; (3) after the pre-sintering in the step (2)Mixing the materials with nano titanium dioxide, and roasting at the constant temperature of 500-900 ℃ for 6-12 h in an inert atmosphere to obtain the final NaTi2(PO4)3‑TiO2a/C composite electrode material. NaTi prepared by the invention2(PO4)3‑TiO2the/C composite electrode material has excellent rate performance and cycle performance, and the production process is easy to control and the cost is low.
Description
Technical field
The invention belongs to electrode materials to synthesize field, and in particular to kind NaTi2(PO4)3-TiO2/ C combination electrode material
Preparation method and application.
Background technique
As lithium ion battery is widely used in electric car field, the demand of lithium is greatly increased, and lithium is in the earth's crust
Reserves it is limited and be unevenly distributed, the raising of lithium ion battery cost certainly will be will cause, this is for development and application in intelligent electricity
It is a bottleneck for the extensive energy-storage battery of net and renewable resource.Sodium and lithium have similar physical and chemical performance, together
When in the earth's crust rich content and widely distributed, sodium-ion battery be considered as the novel secondary that most probable replaces lithium ion battery
One of battery.Since the electrode potential (- 2.7V) of sodium is 0.3V higher than the electrode potential (- 3.04V) of lithium, and the radius of sodium ion is remote
Greater than the radius of lithium ion, cause the migration of sodium ion than lithium ion difficulty；Therefore, to storage sodium needed for sodium-ion battery system
Critical material causes extensive concern.
NASICON type NaTi2(PO4)3With three-dimensional reticular structure, Na+Can be migrated in its three-dimensional channel, be sodium from
The sub- ideal negative electrode material of battery system, however the TiO due to being separated from each other in crystal structure6Octahedron causes NaTi2(PO4)3
Electric conductivity it is poor, chemical property of the material as anode material of lithium-ion battery has been seriously affected, especially in high electricity
Cyclical stability under current density.By carbon-coated NaTi2(PO4)3The electronic conductivity of material can not only be improved, improved
Active material utilization, moreover it is possible to avoid active material from directly contacting with electrolyte, prevent the generation of side reaction, to improve electrode
The cyclical stability of material.But only by material with carbon-coated surface, far from meeting sodium-ion battery to NaTi2(PO4)3High power
Chemical property requirement under rate.
Summary of the invention
In view of this, the present invention is directed to propose a kind of NaTi2(PO4)3-TiO2The preparation method of/C combination electrode material and
Using, with overcome the deficiencies in the prior art, the NaTi prepared using this method2(PO4)3-TiO2/ C combination electrode material has excellent
Different high rate performance and cycle performance, and production process is easy to control, low in cost.
In order to achieve the above objectives, the technical scheme of the present invention is realized as follows:
A kind of NaTi2(PO4)3-TiO2The preparation method of/C combination electrode material, includes the following steps,
(1) sodium source, titanium source, phosphorus source are mixed, and carbon source and solvent progress ball milling dispersion is added, then by ball milling
Slurry afterwards is spray-dried, and spraying presoma is obtained；
(2) by the spraying presoma in step (1) in an inert atmosphere in 250~500 DEG C of 2~6h of progress pre-burning；
(3) material after the pre-burning in step (2) is mixed with nano-titanium dioxide, and under an inert atmosphere, in
Final NaTi is obtained after 500~900 DEG C of 6~12h of constant temperature calcining2(PO4)3-TiO2/ C combination electrode material.
Preferably, in step (1), sodium source, titanium source, phosphorus source according to elemental lithium, ferro element and P elements molar ratio
0.95~1.05:1.9~2.1:2.85~3.15 are mixed；Granularity after ball milling dispersion is 500-900nm；It is described spraying dry
Dry intake air temperature is 220~340 DEG C, and air outlet temperature is 70~120 DEG C.
Preferably, in step (2) and step (3), inert atmosphere is one or both of nitrogen, argon gas or carbon dioxide
It is provided above.
Preferably, in step (3), the nano-titanium dioxide partial size is 200~700nm, and crystal form includes unformed, rutile titania
One or more of mine type, rutile-type；The material after pre-burning in nano-titanium dioxide and step (2) is in mass ratio
5~50% are mixed.
Preferably, in step (1), the sodium source includes sodium bicarbonate, sodium carbonate, sodium sulphate, sodium dihydrogen phosphate, sodium chloride
One or more of；The titanium source include titanium tetrachloride, titanium dioxide, titanium sulfate, isopropyl titanate, in tetraethyl titanate
One or more；Phosphorus source includes phosphoric acid, dihydrogen phosphate, ammonium dihydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate
One or more；
Preferably, in step (1), the carbon source includes graphene, carbon nanotube, sucrose, glucose, aquadag, carbon black
One or more of Super-p, graphite KS-6, PEG；Solvent include water, ethyl alcohol, isopropanol, acetone, in espeleton
It is one or more；The amount that the carbon source is added is the 5~20% of presoma gross mass；The additional amount of solvent is the total matter of presoma
The 30~80% of amount.
The present invention also provides NaTi as described above2(PO4)3-TiO2What the preparation method of/C combination electrode material obtained
NaTi2(PO4)3-TiO2/ C combination electrode material.
Present invention simultaneously provides a kind of cathode, the NaTi obtained including preparation method as described above2(PO4)3-TiO2/C
Combination electrode material.
The present invention also provides a kind of lithium ion battery, the NaTi obtained including preparation method as described above2(PO4)3-
TiO2/ C combination electrode material.
Compared with the existing technology, NaTi of the present invention2(PO4)3-TiO2The preparation method of/C combination electrode material and
Using having the advantage that
The present invention passes through high temperature solid-state method for NaTi2(PO4)3With TiO2, carbon two-layer compound, TiO2Theoretical specific capacity be up to
335mAh/g, and TiO2Layer can promote Na+Migration and enhancing NaTi2(PO4)3The stability of ion surface, and carbon-coating effectively mentions
The high electric conductivity of material, the NaTi prepared using this method2(PO4)3-TiO2/ C combination electrode material has excellent times
Rate performance and cycle performance, and production process is easy to control, low in cost.
The NaTi that preparation method obtains through the invention2(PO4)3-TiO2The battery of/C combination electrode material preparation, in 10C
Under multiplying power, discharge capacity is 92.3mAh/g or more, and capacity retention ratio is 95.2% or more after circulation 2000 weeks.
Detailed description of the invention
Fig. 1 is the XRD diagram of titanium phosphate sodium material prepared by the embodiment of the present invention 1；
Fig. 2 is the SEM figure of titanium phosphate sodium material prepared by the embodiment of the present invention 1；
Fig. 3 is the SEM figure of titanium phosphate sodium material prepared by the embodiment of the present invention 4.
Wherein, XRD diagram shows NaTi in Fig. 12(PO4)3-TiO2The corresponding peak position of/C composite diffraction maximum and PDF card
33-1296 data are consistent, and due to carbon content about 10%, can detecte the peak position of faint carbon.
SEM figure is as can be seen that primary particle size is 200~500nm, coated with carbon bed in Fig. 2.
Specific embodiment
In addition to being defined, technical term used in following embodiment has universal with those skilled in the art of the invention
The identical meanings of understanding.Test reagent used in following embodiment is unless otherwise specified conventional biochemical reagent；It is described
Experimental method is unless otherwise specified conventional method.
Below with reference to embodiment, the present invention will be described in detail.
Embodiment 1
Sodium dihydrogen phosphate, titanium dioxide, ammonium dihydrogen phosphate are mixed according to Na:Ti:P molar ratio for 1.04:2:3,
And it is separately added into PEG and electrically conductive graphite according to 8% and 7% of presoma gross mass, then according to the 30% of presoma gross mass
Deionized water progress ball milling is added and is dispersed to granularity D50=700nm, takes out slurry and is dried to obtain forerunner by spraying with enclosed
Body, intake air temperature are arranged 245 DEG C, and air outlet temperature is arranged 80 DEG C；By presoma in N2Atmosphere under in 350 DEG C of pre-burning 2h,
Then by the 5%TiO of pre-burning material and substance gross mass2Carry out it is uniformly mixed, and in N2Atmosphere under in 550 DEG C of constant temperature calcinings
10h obtains final NaTi2(PO4)3-TiO2/ C composite.
The preparation and test of battery: by obtained NaTi2(PO4)3-TiO2/ C composite is according to active material: conductive
Agent: the mixing of binder=8:1:1 ratio uniform, wherein conductive agent is Super-p, binder PVDF；By mixed object
Material is coated on collector Thin Stainless Steel on piece, and after drying, the cathode of battery is made；By lithium manganate material according to active material: leading
Electric agent 1: conductive agent 2: (wherein conductive agent 1 is Super-p to binder=75:10:5:10；Conductive agent 2 is carbon nanotube；Bonding
Agent is PVDF) ratio uniform mixing, be coated in collector titanium net, after drying, the anode of battery be made.With non-woven fabrics be every
Film, the Na of 1mol/L2SO4Solution is assembled into button cell as electrolyte.
Test result: using the NaTi of the present embodiment2(PO4)3-TiO2/ C composite is under 10C multiplying power, discharge capacity
For 92.3mAh/g, capacity retention ratio is 95.2% after recycling 2000 weeks.
Embodiment 2
Sodium dihydrogen phosphate, titanium dioxide are mixed according to Na:Ti:P molar ratio for 1.04:2:3, and according to presoma
The 8% of gross mass and 7% is separately added into PEG and electrically conductive graphite, and deionized water then is added according to the 30% of presoma gross mass
It carries out ball milling and is dispersed to granularity D50=750nm, take out slurry and be dried to obtain presoma, intake air temperature by spraying with enclosed
245 DEG C of setting, air outlet temperature are arranged 80 DEG C；By presoma in N2Atmosphere under in 350 DEG C of pre-burning 2h, then by pre-burning material
With the 8%TiO of substance gross mass2Carry out it is uniformly mixed, and in N2Atmosphere under in 550 DEG C of constant temperature calcining 10h, obtain final
NaTi2(PO4)3-TiO2/ C composite.
The preparation and test of battery are the same as embodiment 1.
Test result: using the NaTi of the present embodiment2(PO4)3-TiO2/ C composite is under 10C multiplying power, discharge capacity
For 93.7mAh/g, capacity retention ratio is 95.8% after recycling 2000 weeks.
Embodiment 3
Sodium carbonate, titanium dioxide, ammonium dihydrogen phosphate are mixed according to Na:Ti:P molar ratio for 1.05:2:3, and pressed
Glucose is added according to the 14% of presoma gross mass, deionized water then is added according to the 40% of presoma gross mass and carries out ball milling
It is dispersed to granularity D50=750nm, slurry is taken out and is dried to obtain presoma, intake air temperature setting 250 by spraying with enclosed
DEG C, air outlet temperature is arranged 75 DEG C；By presoma in N2Atmosphere under in 300 DEG C of pre-burning 3h, then by pre-burning material and substance
The 8%TiO of gross mass2Carry out it is uniformly mixed, and in N2Atmosphere under in 600 DEG C of constant temperature calcining 9h, obtain final NaTi2
(PO4)3-TiO2/ C composite.
The preparation and test of battery are the same as embodiment 1.
Test result: using the NaTi of the present embodiment2(PO4)3-TiO2/ C composite is under 10C multiplying power, discharge capacity
For 95.4mAh/g, capacity retention ratio is 95.5% after recycling 2000 weeks.
Embodiment 4
Sodium dihydrogen phosphate, titanium dioxide, ammonium dihydrogen phosphate are mixed according to Na:Ti:P molar ratio for 1.055:2:3,
And it is separately added into sucrose and electrically conductive graphite according to 10% and 3% of presoma gross mass, then according to presoma gross mass
40% addition deionized water carries out ball milling and is dispersed to granularity D50=750nm, takes out slurry and is dried before obtaining by spraying with enclosed
Body is driven, intake air temperature is arranged 250 DEG C, and air outlet temperature is arranged 75 DEG C；By presoma in N2Atmosphere under in 350 DEG C of pre-burnings
2h, then by the 10%TiO of pre-burning material and substance gross mass2Carry out it is uniformly mixed, and in N2Atmosphere under in 650 DEG C of constant temperature
9.5h is roasted, final NaTi is obtained2(PO4)3-TiO2/ C composite.
The preparation and test of battery are the same as embodiment 1.
Test result: using the NaTi of the present embodiment2(PO4)3-TiO2/ C composite is under 10C multiplying power, discharge capacity
For 93.8mAh/g, capacity retention ratio is 96.4% after recycling 2000 weeks.
Embodiment 5
Sodium hydroxide, titanium dioxide, ammonium dihydrogen phosphate are mixed according to Na:Ti:P molar ratio for 1.06:2:3, and
It is separately added into PEG and electrically conductive graphite according to 10% and 3% of presoma gross mass, is then added according to the 30% of presoma gross mass
Enter deionized water progress ball milling and be dispersed to granularity D50=800nm, takes out slurry and be dried to obtain presoma by spraying with enclosed,
Intake air temperature is arranged 245 DEG C, and air outlet temperature is arranged 80 DEG C；By presoma in N2Atmosphere under in 350 DEG C of pre-burning 2h, then
By the 15%TiO of pre-burning material and substance gross mass2Carry out it is uniformly mixed, and in N2Atmosphere under in 800 DEG C of constant temperature calcining 9h,
Obtain final NaTi2(PO4)3-TiO2/ C composite.
The preparation and test of battery are the same as embodiment 1.
Test result: using the NaTi of the present embodiment2(PO4)3-TiO2/ C composite is under 10C multiplying power, discharge capacity
For 97.2mAh/g, capacity retention ratio is 96% after recycling 2000 weeks.
Comparative example 1
Sodium dihydrogen phosphate, titanium dioxide, ammonium dihydrogen phosphate are mixed according to molar ratio 1.025:2:3.15, and according to
Glucose is added in the 15% of material gross mass, and a small amount of dispersant A A4040 is added, after according to material gross mass 40% plus water into
Row high speed dispersion obtains material A；Material A is subjected to ball milling, slurry is taken out after 3h, obtains material B, material B is sprayed with enclosed
It is dried, intake air temperature is arranged 260 DEG C, and air outlet temperature is arranged 90 DEG C, obtains material C；By material C in N2Atmosphere under
With 2.5 DEG C/min heating, and acetylene gas is passed through with the flowing velocity of 1L/min, in 800 DEG C of heat preservation 8h, obtains carbon modification
NaTi2(PO4)3/ C composite negative pole material.
The preparation and test of battery are the same as embodiment 1.
Test result: using the NaTi of the present embodiment2(PO4)3-TiO2/ C composite is under 10C multiplying power, discharge capacity
For 81.5mAh/g, capacity retention ratio is 85.4% after recycling 1000 weeks.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Within mind and principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (9)
1. a kind of NaTi2(PO4)3-TiO2The preparation method of/C combination electrode material, it is characterised in that: include the following steps,
(1) sodium source, titanium source, phosphorus source are mixed, and carbon source and solvent progress ball milling dispersion is added, it then will be after ball milling
Slurry is spray-dried, and spraying presoma is obtained；
(2) by the spraying presoma in step (1) in an inert atmosphere in 250~500 DEG C of 2~6h of progress pre-burning；
(3) material after the pre-burning in step (2) is mixed with nano-titanium dioxide, and under an inert atmosphere, in 500~
Final NaTi is obtained after 900 DEG C of 6~12h of constant temperature calcining2(PO4)3-TiO2/ C combination electrode material.
2. NaTi according to claim 12(PO4)3-TiO2The preparation method of/C combination electrode material, it is characterised in that:
In step (1), sodium source, titanium source, phosphorus source according to elemental lithium, ferro element and P elements molar ratio be 0.95~1.05:1.9~
2.1:2.85~3.15 are mixed；Granularity after ball milling dispersion is 500-900nm；The intake air temperature of the spray drying is
220~340 DEG C, air outlet temperature is 70~120 DEG C.
3. NaTi according to claim 12(PO4)3-TiO2The preparation method of/C combination electrode material, it is characterised in that:
In step (2) and step (3), inert atmosphere is that one or more of nitrogen, argon gas or carbon dioxide provide.
4. NaTi according to claim 12(PO4)3-TiO2The preparation method of/C combination electrode material, it is characterised in that:
In step (3), the nano-titanium dioxide partial size is 200~700nm, and crystal form includes unformed, Detitanium-ore-type, in rutile-type
One or more；Nano-titanium dioxide is mixed with the material in mass ratio 5~50% after the pre-burning in step (2)
It closes.
5. NaTi according to claim 12(PO4)3-TiO2The preparation method of/C combination electrode material, it is characterised in that:
In step (1), the sodium source includes one or both of sodium bicarbonate, sodium carbonate, sodium sulphate, sodium dihydrogen phosphate, sodium chloride
More than；The titanium source include one or both of titanium tetrachloride, titanium dioxide, titanium sulfate, isopropyl titanate, tetraethyl titanate with
On；Phosphorus source include phosphoric acid, dihydrogen phosphate, ammonium dihydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate it is one or two kinds of with
On.
6. NaTi according to claim 12(PO4)3-TiO2The preparation method of/C combination electrode material, it is characterised in that:
In step (1), the carbon source includes graphene, carbon nanotube, sucrose, glucose, aquadag, carbon black Super-p, graphite KS-
6, one or more of PEG；Solvent includes one of water, ethyl alcohol, isopropanol, acetone, espeleton or a variety of；Institute
The amount for stating carbon source addition is the 5~20% of presoma gross mass；The additional amount of solvent is the 30~80% of presoma gross mass.
7. NaTi as described in any one of claims 1 to 62(PO4)3-TiO2What the preparation method of/C combination electrode material obtained
NaTi2(PO4)3-TiO2/ C combination electrode material.
8. a kind of cathode, it is characterised in that: the NaTi obtained including the described in any item preparation methods of claim 1~72
(PO4)3-TiO2/ C combination electrode material.
9. a kind of lithium ion battery, it is characterised in that: obtained including the described in any item preparation methods of claim 1~7
NaTi2(PO4)3-TiO2/ C combination electrode material.
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