CN116902949A - Preparation method of sodium ion battery composite material - Google Patents
Preparation method of sodium ion battery composite material Download PDFInfo
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- CN116902949A CN116902949A CN202310758615.XA CN202310758615A CN116902949A CN 116902949 A CN116902949 A CN 116902949A CN 202310758615 A CN202310758615 A CN 202310758615A CN 116902949 A CN116902949 A CN 116902949A
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- Prior art keywords
- sodium
- sintering
- area
- ball milling
- ion battery
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- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 42
- 239000002131 composite material Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 238000005245 sintering Methods 0.000 claims abstract description 62
- 238000000498 ball milling Methods 0.000 claims abstract description 55
- 238000006243 chemical reaction Methods 0.000 claims abstract description 47
- 239000000463 material Substances 0.000 claims abstract description 38
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000001816 cooling Methods 0.000 claims abstract description 30
- 238000003756 stirring Methods 0.000 claims abstract description 20
- 230000007246 mechanism Effects 0.000 claims abstract description 19
- 230000005540 biological transmission Effects 0.000 claims abstract description 15
- 229910052751 metal Inorganic materials 0.000 claims abstract description 14
- 239000002184 metal Substances 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 13
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 13
- 239000011734 sodium 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 12
- 229910052742 iron Inorganic materials 0.000 claims abstract description 11
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000012298 atmosphere Substances 0.000 claims abstract description 8
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 8
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 8
- 239000011574 phosphorus Substances 0.000 claims abstract description 8
- 230000001737 promoting effect Effects 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 239000005955 Ferric phosphate Substances 0.000 claims description 7
- 229940032958 ferric phosphate Drugs 0.000 claims description 7
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 claims description 7
- 229910000399 iron(III) phosphate Inorganic materials 0.000 claims description 7
- 238000004321 preservation Methods 0.000 claims description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 5
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 5
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 5
- 229910052720 vanadium Inorganic materials 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 239000007774 positive electrode material Substances 0.000 claims description 4
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 3
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 3
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 3
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 3
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 3
- 239000001488 sodium phosphate Substances 0.000 claims description 3
- 235000011008 sodium phosphates Nutrition 0.000 claims description 3
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims description 3
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 3
- MOMKYJPSVWEWPM-UHFFFAOYSA-N 4-(chloromethyl)-2-(4-methylphenyl)-1,3-thiazole Chemical compound C1=CC(C)=CC=C1C1=NC(CCl)=CS1 MOMKYJPSVWEWPM-UHFFFAOYSA-N 0.000 claims description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- 239000004280 Sodium formate Substances 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 2
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 2
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 2
- 229910000397 disodium phosphate Inorganic materials 0.000 claims description 2
- 235000019800 disodium phosphate Nutrition 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 238000012545 processing Methods 0.000 claims description 2
- 239000001632 sodium acetate Substances 0.000 claims description 2
- 235000017281 sodium acetate Nutrition 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- 239000001509 sodium citrate Substances 0.000 claims description 2
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 2
- 235000011083 sodium citrates Nutrition 0.000 claims description 2
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 claims description 2
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 claims description 2
- 235000019254 sodium formate Nutrition 0.000 claims description 2
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 2
- 235000019983 sodium metaphosphate Nutrition 0.000 claims description 2
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 claims description 2
- 229940039790 sodium oxalate Drugs 0.000 claims description 2
- 229940048086 sodium pyrophosphate Drugs 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 235000019818 tetrasodium diphosphate Nutrition 0.000 claims description 2
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 13
- 229910052799 carbon Inorganic materials 0.000 description 13
- AWRQDLAZGAQUNZ-UHFFFAOYSA-K sodium;iron(2+);phosphate Chemical compound [Na+].[Fe+2].[O-]P([O-])([O-])=O AWRQDLAZGAQUNZ-UHFFFAOYSA-K 0.000 description 12
- 230000008569 process Effects 0.000 description 8
- 230000009467 reduction Effects 0.000 description 7
- 230000003068 static effect Effects 0.000 description 6
- 239000002002 slurry Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 239000010405 anode material Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000011149 active material Substances 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- -1 sodium iron phosphate-sodium vanadium phosphate Chemical compound 0.000 description 2
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 2
- 239000005696 Diammonium phosphate Substances 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000006012 monoammonium phosphate Substances 0.000 description 1
- JOUIQRNQJGXQDC-AXTSPUMRSA-N namn Chemical compound O1[C@@H](COP(O)([O-])=O)[C@H](O)[C@@H](O)[C@@H]1[N+]1=CC=CC(C(O)=O)=C1 JOUIQRNQJGXQDC-AXTSPUMRSA-N 0.000 description 1
- 239000010450 olivine Substances 0.000 description 1
- 229910052609 olivine Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000447 polyanionic polymer Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- XWQGIDJIEPIQBD-UHFFFAOYSA-J sodium;iron(3+);phosphonato phosphate Chemical compound [Na+].[Fe+3].[O-]P([O-])(=O)OP([O-])([O-])=O XWQGIDJIEPIQBD-UHFFFAOYSA-J 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/45—Phosphates containing plural metal, or metal and ammonium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/18—Stationary reactors having moving elements inside
- B01J19/20—Stationary reactors having moving elements inside in the form of helices, e.g. screw reactors
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F27—FURNACES; KILNS; OVENS; RETORTS
- F27B—FURNACES, KILNS, OVENS, OR RETORTS IN GENERAL; OPEN SINTERING OR LIKE APPARATUS
- F27B19/00—Combinations of furnaces of kinds not covered by a single preceding main group
- F27B19/04—Combinations of furnaces of kinds not covered by a single preceding main group arranged for associated working
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F27—FURNACES; KILNS; OVENS; RETORTS
- F27D—DETAILS OR ACCESSORIES OF FURNACES, KILNS, OVENS, OR RETORTS, IN SO FAR AS THEY ARE OF KINDS OCCURRING IN MORE THAN ONE KIND OF FURNACE
- F27D9/00—Cooling of furnaces or of charges therein
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F27—FURNACES; KILNS; OVENS; RETORTS
- F27D—DETAILS OR ACCESSORIES OF FURNACES, KILNS, OVENS, OR RETORTS, IN SO FAR AS THEY ARE OF KINDS OCCURRING IN MORE THAN ONE KIND OF FURNACE
- F27D9/00—Cooling of furnaces or of charges therein
- F27D2009/007—Cooling of charges therein
- F27D2009/0072—Cooling of charges therein the cooling medium being a gas
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F27—FURNACES; KILNS; OVENS; RETORTS
- F27M—INDEXING SCHEME RELATING TO ASPECTS OF THE CHARGES OR FURNACES, KILNS, OVENS OR RETORTS
- F27M2003/00—Type of treatment of the charge
- F27M2003/04—Sintering
-
- 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)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Mechanical Engineering (AREA)
- Inorganic Chemistry (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- General Engineering & Computer Science (AREA)
- Crystallography & Structural Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a preparation method of a sodium ion battery composite material, which comprises the steps of taking a phosphorus source, an iron source and a sodium source as reaction raw materials, taking nano metal as a reducing agent, adding the raw materials into a reaction furnace according to a set proportion, and sequentially performing ball milling, sintering and cooling under an inert atmosphere to obtain the sodium ion battery composite material; the reaction furnace comprises a ball milling area, a sintering area and a cooling area from left to right in sequence, the reaction furnace is transversely arranged and can rotate around a central shaft, a first sieve plate is arranged between the ball milling area and the sintering area, and a second sieve plate is arranged between the sintering area and the cooling area; the aperture of the sieve holes on the first sieve plate is smaller than the minimum diameter of the ball milling medium; a driving motor is arranged on the right side of the reaction furnace, and a transmission shaft of the driving motor is positioned at the central shaft position of the reaction furnace; the transmission shaft penetrates through the side wall of the reaction furnace and extends to the sintering zone through the second sieve plate; the part of the transmission shaft, which is positioned in the sintering zone, is provided with a stirring mechanism which can be used for dispersing materials and promoting the materials to advance.
Description
Technical Field
The invention relates to the technical field of sodium ion batteries, in particular to a preparation method of a sodium ion battery composite material.
Background
Among the positive electrode materials of sodium ion batteries, polyanion compounds are considered as a type of electrode materials with the most promising application prospect due to their excellent structural stability, safety and suitable voltage plateau. Wherein, the sodium iron phosphate material has rich raw materials, low price, three-dimensional ion diffusion channel, good safety performance and sodium iron phosphate NaFePO 4 Are preferentially considered as sodium ion battery cathode materials. NaFePO of olivine structure 4 The theoretical specific capacity of the cathode material of the sodium ion battery is 154mAh/g.
CN105161688A discloses a carbon-coated sodium iron phosphate-sodium vanadium phosphate composite material and a preparation method thereof, wherein iron vanadate is prepared, and then the iron vanadate is used as a raw material to obtain the carbon-coated sodium iron phosphate-sodium vanadium phosphate through the steps of ball milling, regrinding, calcining and the like. The first charge-discharge gram capacity of the obtained material is 101.8 mAh.g under the 1C multiplying power within the voltage range of 2.0-4.0V -1 The method comprises the steps of carrying out a first treatment on the surface of the After 50 cycles of 1C during charge and discharge, the capacity retention rate was 96.5%.
CN115148976a discloses a method for synthesizing sodium ion battery anode material ferric sodium phosphate/carbon and sodium ion battery, which comprises the following steps: adding deionized water into organic phosphonic acid, organic sodium acid, nano ferric phosphate and a sodium source, stirring, heating, stirring, evaporating to dryness, drying, grinding, presintering under nitrogen protection, naturally cooling, grinding again, sintering under nitrogen protection, and naturally cooling to obtain the sodium ion battery anode material ferric phosphate sodium/carbon. The obtained material is charged and discharged at the multiplying power of 1C within the voltage range of 2.0-4.2V, the material presents a typical sodium ferric pyrophosphate charging and discharging curve, and the initial ring discharging specific capacity is 99.38mAhg -1 The capacity retention after 300 cycles was 94.2%.
In the prior art, carbon reduction is generally adopted for carbon coating or carbon doping in the preparation process of sodium iron phosphate so as to improve the conductivity of the sodium iron phosphate, environmental pollution is easily caused by carbon reduction, and the prepared sodium iron phosphate has the problems of lower specific capacity and faster capacity decay after circulation; in the current industrial production process, the sodium iron phosphate material adopts a static sintering method, the static sintering has unstable sintering control, is easy to generate over-sintering condition, has incomplete reaction, and has larger prepared material particles and lower production efficiency.
Disclosure of Invention
Aiming at the problems of carbon coating or carbon doping by commonly adopting carbon reduction in the preparation process of sodium iron phosphate so as to improve the conductivity of sodium iron phosphate, environment pollution is easily caused by carbon reduction, the prepared sodium iron phosphate has the problems of lower specific capacity and quicker capacity decay after circulation, the static sintering method is adopted as the sodium iron phosphate material in the current industrial production process, the static sintering has unstable sintering control and is easy to generate over-sintering condition, the reaction is incomplete, the prepared material particles are larger, and the production efficiency is lower.
The invention provides a preparation method of a sodium ion battery composite material, which comprises the steps of taking a phosphorus source, an iron source and a sodium source as reaction raw materials, taking nano metal as a reducing agent, adding the raw materials into a reaction furnace according to a set proportion, and sequentially performing ball milling, sintering and cooling in an inert atmosphere to obtain the sodium ion battery composite material;
the chemical formula of the sodium ion battery composite material is NaM x Fe y PO 4 0 < x < 1,0 < y < 1, M is selected from one or more of Mg, al, ti, V, mn, zn, cr;
the reaction furnace sequentially comprises a ball milling area, a sintering area and a cooling area from left to right, wherein a feed inlet is arranged above the ball milling area, and a discharge outlet is arranged below the cooling area; the reaction furnace is transversely arranged and can rotate around a central shaft, a first sieve plate is arranged between the ball milling area and the sintering area, and a second sieve plate is arranged between the sintering area and the cooling area; the aperture of the sieve holes on the first sieve plate is smaller than the minimum diameter of the ball milling medium;
a driving motor is arranged on the right side of the reaction furnace, and a transmission shaft of the driving motor is positioned at the central shaft position of the reaction furnace; the transmission shaft penetrates through the side wall of the reaction furnace and extends to the sintering zone through the second sieve plate; the part of the transmission shaft, which is positioned in the sintering zone, is provided with a stirring mechanism which can be used for dispersing materials and promoting the materials to advance.
In a specific embodiment, the stirring mechanism is any one of a spiral stirrer and a gear stirrer. Through setting up rabbling mechanism, keep the material dispersion even at the sintering process, prevent local overburning, the material granule of preparation is less, and production efficiency is high.
In a specific embodiment, the drive shaft is connected to the second screen plate by means of bearings. When the furnace body of the reaction furnace drives the second sieve plate to rotate, the stirring mechanism is connected with the driving motor through the transmission shaft, and the stirring mechanism is not mutually interfered.
In a specific embodiment, a rotary gear is arranged on the right side of the furnace body of the reaction furnace, a power device is arranged on the side face of the furnace body, and the rotary gear is connected with the power device through a chain so that the furnace body rotates relative to the stirring mechanism.
In a specific embodiment, the heights of the bottoms of the ball milling area and the sintering area are reduced from left to right in sequence to form a slope, so that the materials are conveyed from left to right.
In a specific embodiment, the ball milling medium adopted by the ball milling area is one or more of metal and ceramic; the ball milling medium is spherical or cylindrical in shape; the ball milling media are uniform or multiple in size, namely the ball milling media are of the same size specification, or the ball milling media are formed by mixing the ball milling media of multiple sizes. The material, shape and size of the ball milling medium can be selected according to the needs to meet the crushing needs of materials.
In a specific embodiment, the phosphorus source is one or more of monoammonium phosphate, diammonium phosphate, sodium dihydrogen phosphate, and phosphorus pentoxide;
the iron source is one or more of ferric phosphate and ferric oxide;
the sodium source is one or more of sodium carbonate, sodium bicarbonate, sodium hydroxide, sodium acetate, sodium phosphate, sodium hydrogen phosphate, sodium oxalate, sodium formate, sodium citrate, sodium pyrophosphate and sodium metaphosphate.
In a specific embodiment, an inert gas inlet is provided above the ball milling zone. The ball milling process of the mixed product needs to be carried out in inert atmosphere to prevent the nano metal from being oxidized and influence the reduction performance of the nano metal.
In a specific embodiment, the inert atmosphere is any one of nitrogen, argon and helium.
In a specific embodiment, a discharge port of the cooling zone is provided with a circulation unit, and materials to be processed are returned to the ball milling zone for circulation processing.
In a specific embodiment, the side wall of the sintering zone is provided with a heating unit, and the sintering temperature is controlled by a controller.
In a specific embodiment, the sintering process adopts sectional sintering, the sintering temperature is 300-800 ℃, and the material heat preservation time is 0.5-12 h.
In a specific embodiment, the cooling area is movably connected with the sintering area, and the cooling area is kept static when the ball milling area and the sintering area are driven to rotate by the power device.
The invention also provides application of the preparation method of the sodium ion battery composite material in preparation of a sodium battery anode material.
Compared with the prior art, the invention has the beneficial technical effects that:
(1) According to the preparation method, nano metal Mg, al, ti, zr, V, mn, zn, cr powder is selected as a reducing agent according to the metal activity sequence Mg, al, ti, zr, V, mn, zn, cr which is larger than Fe, high-valence iron is reduced, raw materials are fully mixed by utilizing a ball mill under inert atmosphere, and the reactivity is improved.
(2) The invention provides a preparation method of a sodium ion battery composite material, which comprises the steps of ball milling, sintering and cooling materials through a reaction furnace, so that the materials are fully mixed, and the materials are fully reacted and synthesized; compared with the existing static sintering technology, the method can effectively control the synthesis speed, temperature and time of materials in the furnace body, so that the product can show good electrochemical stability, and has high charge and discharge capacity and good cycle performance.
(3) The invention provides a preparation method of a sodium ion battery composite material, which adopts a carbon-free reduction-low temperature synthesis process, has simple process, low synthesis temperature, short reaction time and full synthesis reaction at low temperature, and can effectively save energy and reduce emission by adopting carbon-free reduction, thereby reducing the product cost.
Drawings
FIG. 1 is a schematic structural diagram of a reaction furnace used in a method for preparing a sodium ion battery composite material according to the present invention;
FIG. 2 is a schematic structural view of a first screen plate and a second screen plate in a reaction furnace;
FIG. 3 is another structure of the stirring mechanism in the reaction furnace;
FIG. 4 shows NaV as a sodium ion battery composite material in example 1 of the present invention 0.2 Fe 0.7 PO 4 SEM images of (a).
In the figure, a 1-ball milling zone; 2-a sintering zone; 3-a cooling zone; 4-a feed inlet; 5-a discharge hole; 6-a first sieve plate; 7-a second sieve plate; 8-driving a motor; 9-a transmission shaft; 10-a stirring mechanism; 11-a bearing; 12-rotating a gear; 13-a power plant; 14-inert gas inlet; 15-a heating unit.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below, and it is apparent that the described embodiments are only some embodiments, but not all embodiments of the present invention, and all other embodiments obtained by those skilled in the art without making any inventive effort based on the embodiments of the present invention are within the scope of protection of the present invention.
The reagents used in this example are all common commercial products or prepared by conventional means, and the equipment used is conventional in the art, and the following are some examples of the inventors in experiments:
example 1
NaV (sodium ion battery) composite material 0.2 Fe 0.7 PO 4 The preparation method of (2) comprises the following steps:
s1, taking ammonium dihydrogen phosphate, ferric oxide and sodium carbonate as reaction raw materials, taking metal vanadium powder as a reducing agent, and adding the metal vanadium powder into a reaction furnace according to the molar ratio of sodium, vanadium, iron and phosphorus being 1:0.2:0.7:1;
and S2, sequentially performing ball milling, sintering and cooling under nitrogen, wherein the sintering temperature is 600 ℃, and the heat preservation time is 4 hours, so as to obtain the sodium ion battery composite material. FIG. 4 shows NaV as a sodium ion battery composite material in example 1 of the present invention 0.2 Fe 0.7 PO 4 SEM images of (a).
As shown in fig. 1-3, the reaction furnace sequentially comprises a ball milling area 1, a sintering area 2 and a cooling area 3 from left to right, wherein a feed inlet 4 is arranged above the ball milling area 1, and a discharge outlet 5 is arranged below the cooling area 3; the reaction furnace is transversely arranged and can rotate around a central shaft, a first sieve plate 6 is arranged between the ball milling area 1 and the sintering area 2, and a second sieve plate 7 is arranged between the sintering area 2 and the cooling area 3; the aperture of the sieve holes on the first sieve plate 6 is smaller than the minimum diameter of the ball milling medium; the heights of the bottoms of the ball milling area 1 and the sintering area 2 are reduced from left to right in sequence to form a slope, which is beneficial to the left-to-right conveying of materials.
A driving motor 8 is arranged on the right side of the reaction furnace, and a transmission shaft 9 of the driving motor 8 is positioned at the central shaft position of the reaction furnace; the transmission shaft 9 passes through the side wall of the reaction furnace and extends to the sintering zone 2 through the second sieve plate 7; the part of the transmission shaft 9 located in the sintering zone is provided with a stirring mechanism, and the stirring mechanism 10 can be used for dispersing materials and promoting the materials to advance.
In this embodiment, the stirring mechanism 10 is a spiral stirrer, and by setting the stirring mechanism, the materials are kept uniformly dispersed in the sintering process, local overburning is prevented, and the prepared material particles are smaller and have high production efficiency.
In this embodiment, the drive shaft 9 is connected to the second screening deck 7 by means of bearings 11. When the furnace body of the reaction furnace drives the second sieve plate 7 to rotate, the spiral stirrer is connected with the driving motor 8 through the transmission shaft 9, and the spiral stirrer is not mutually interfered.
In this embodiment, a rotary gear 12 is disposed at the right side of the furnace body of the reaction furnace, a power device 13 is disposed at the side of the furnace body, and the rotary gear 12 is connected with the power device 13 through a chain so as to enable the furnace body to rotate relative to the stirring mechanism.
In the embodiment, the ball milling area adopts ceramic ball milling medium, and the shape of the ball milling medium is spherical or cylindrical; the ball milling media are uniform or multiple in size, namely the ball milling media are of the same size specification, or the ball milling media are formed by mixing the ball milling media of multiple sizes.
In this embodiment, an inert gas inlet 14 is provided above the ball milling zone 1. The ball milling process of the mixed product needs to be carried out in inert atmosphere to prevent the nano metal from being oxidized and influence the reduction performance of the nano metal.
In this embodiment, the side wall of the sintering zone 2 is provided with a heating unit 15, and the sintering temperature is controlled by a controller.
In this embodiment, the cooling area 3 is movably connected with the sintering area 2, and the cooling area 3 is kept stationary when the power device 13 drives the ball milling area 1 and the sintering area 2 to rotate.
The working process of the reaction furnace comprises the following steps: firstly, a power device 13 is started to drive a furnace body to rotate, materials in a ball milling area 1 are ball milled, the materials enter a sintering area 2 through a first sieve plate 6 after being crushed, the ball milled materials are sintered by a heating unit 15, after heat preservation is carried out for a preset time, a stirring mechanism 10 is started, the stirring mechanism can be used for dispersing the materials and can promote the materials to advance, the materials enter a cooling area through a second sieve plate 7, and a sodium ion battery composite material is obtained after cooling.
Example 2
NaAl composite material of sodium ion battery 0.2 Fe 0.7 PO 4 The preparation method of (2) comprises the following steps:
s1, adding sodium dihydrogen phosphate, ferric phosphate and sodium carbonate serving as reaction raw materials and metal aluminum powder serving as a reducing agent into a reaction furnace according to the molar ratio of sodium, aluminum, iron and phosphorus of 1:0.2:0.7:1, wherein the reaction furnace in the embodiment 1 is adopted;
and S2, sequentially performing ball milling, sintering and cooling under nitrogen, wherein the sintering temperature is 600 ℃, and the heat preservation time is 4 hours, so as to obtain the sodium ion battery composite material.
Example 3
NaMn composite material of sodium ion battery 0.3 Fe 0.7 PO 4 The preparation method of (2) comprises the following steps:
s1, adding sodium dihydrogen phosphate, ferric phosphate and sodium carbonate serving as reaction raw materials and metal manganese powder serving as a reducing agent into a reaction furnace according to the molar ratio of sodium, manganese, iron and phosphorus of 1:0.3:0.7:1, wherein the reaction furnace in the embodiment 1 is adopted;
and S2, sequentially performing ball milling, sintering and cooling under nitrogen, wherein the sintering temperature is 600 ℃, and the heat preservation time is 4 hours, so as to obtain the sodium ion battery composite material.
Comparative example 1
Sodium iron phosphate NaFePO 4 A method for preparing a/C active material comprising the steps of:
s1, taking sodium dihydrogen phosphate, ferric phosphate and sodium carbonate as reaction raw materials, and glucose as a reducing agent and a carbon source to obtain a mixed product;
s2, ball milling is carried out on the mixed product obtained in the step S1 under nitrogen for 8 hours, and a ball milling product is obtained;
and S3, placing the ball-milling product obtained in the step S2 into a sintering furnace for calcination under nitrogen, wherein the sintering temperature is 600 ℃, the heat preservation time is 4 hours, and cooling to obtain the sodium iron phosphate active material.
Taking the positive electrode materials of the sodium ion batteries, the polyvinylidene fluoride adhesive and the carbon black conductive agent prepared in the examples 1-3 and the comparative example 1, mixing the positive electrode materials of the sodium ion batteries, the adhesive and the conductive agent according to the mass ratio of 8:1:1, adding a proper amount of N-methyl pyrrolidone to prepare a thick slurry, coating the thick slurry on an aluminum foil with a rough surface, baking the thick slurry in a vacuum drying oven at 80 ℃ for 8 hours, after the thick slurry is completely dried, using a sheet punching machine to prepare a proper whole piece of pole pieceAnd the wafer electrode with the size is ready for use. Sodium metal is used as a counter electrode, glass fiber is used as a diaphragm, and 1mol/LNaClO is used as a diaphragm 4 (EC and DEC in a solvent volume ratio of 1:1) as an electrolyte, a 2016 button cell was assembled in an argon-protected glove box. The batteries were tested in the voltage range of 2.0 to 4.0V and the results are shown in table 1:
table 1 electrochemical performance test data for sodium ion batteries
Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (10)
1. The preparation method of the sodium ion battery composite material is characterized in that a phosphorus source, an iron source and a sodium source are used as reaction raw materials, nano metal is used as a reducing agent, the raw materials are added into a reaction furnace according to a set proportion, ball milling, sintering and cooling are sequentially carried out in an inert atmosphere, and the sodium ion battery composite material is obtained;
the chemical formula of the sodium ion battery composite material is NaM x Fe y PO 4 0 < x < 1,0 < y < 1, M is selected from one or more of Mg, al, ti, V, mn, zn, cr;
the reaction furnace sequentially comprises a ball milling area, a sintering area and a cooling area from left to right, wherein a feed inlet is arranged above the ball milling area, and a discharge outlet is arranged below the cooling area; the reaction furnace is transversely arranged and can rotate around a central shaft, a first sieve plate is arranged between the ball milling area and the sintering area, and a second sieve plate is arranged between the sintering area and the cooling area; the aperture of the sieve holes on the first sieve plate is smaller than the minimum diameter of the ball milling medium;
a driving motor is arranged on the right side of the reaction furnace, and a transmission shaft of the driving motor is positioned at the central shaft position of the reaction furnace; the transmission shaft penetrates through the side wall of the reaction furnace and extends to the sintering zone through the second sieve plate; the part of the transmission shaft, which is positioned in the sintering zone, is provided with a stirring mechanism which can be used for dispersing materials and promoting the materials to advance.
2. The method for producing a sodium ion battery composite material according to claim 1, wherein the stirring mechanism is any one of a screw stirrer and a gear stirrer.
3. The method of claim 1, wherein the drive shaft is coupled to the second screen plate via a bearing.
4. The method for preparing the sodium ion battery composite material according to claim 1, wherein a rotary gear is arranged on the right side of the furnace body of the reaction furnace, a power device is arranged on the side surface of the furnace body, and the rotary gear is connected with the power device through a chain so as to enable the furnace body to rotate relative to the stirring mechanism.
5. The method for preparing a sodium ion battery composite material according to claim 1, wherein the heights of the ball milling area and the bottom of the sintering area are reduced from left to right.
6. The method for preparing a sodium ion battery composite material according to claim 1, wherein the phosphorus source is one or more of ammonium dihydrogen phosphate, diammonium hydrogen phosphate, sodium dihydrogen phosphate and phosphorus pentoxide;
the iron source is one or more of ferric phosphate and ferric oxide;
the sodium source is one or more of sodium carbonate, sodium bicarbonate, sodium hydroxide, sodium acetate, sodium phosphate, sodium hydrogen phosphate, sodium oxalate, sodium formate, sodium citrate, sodium pyrophosphate and sodium metaphosphate.
7. The method for preparing a sodium ion battery composite material according to claim 1, wherein an inert gas inlet is arranged above the ball milling area; the inert atmosphere adopts any one of nitrogen, argon and helium.
8. The method for preparing the sodium ion battery composite material according to claim 1, wherein a discharge port of the cooling zone is provided with a circulation unit, and materials to be processed are returned to the ball milling zone for circulation processing.
9. The method for preparing a sodium ion battery composite material according to claim 1, wherein a heating unit is provided on a side wall of the sintering zone; the sintering temperature is 300-800 ℃, and the material heat preservation time is 0.5-12 h.
10. Use of the method for preparing a sodium ion battery composite material according to any one of claims 1 to 9 in the preparation of a sodium battery positive electrode material.
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