CN115911357A - Preparation method and application of carbon-coated lithium ferrite material - Google Patents
Preparation method and application of carbon-coated lithium ferrite material Download PDFInfo
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- CN115911357A CN115911357A CN202211445225.9A CN202211445225A CN115911357A CN 115911357 A CN115911357 A CN 115911357A CN 202211445225 A CN202211445225 A CN 202211445225A CN 115911357 A CN115911357 A CN 115911357A
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- 239000000463 material Substances 0.000 title claims abstract description 130
- JXGGISJJMPYXGJ-UHFFFAOYSA-N lithium;oxido(oxo)iron Chemical compound [Li+].[O-][Fe]=O JXGGISJJMPYXGJ-UHFFFAOYSA-N 0.000 title claims abstract description 110
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 91
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 83
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 74
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 72
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 50
- 238000005245 sintering Methods 0.000 claims abstract description 40
- 238000000227 grinding Methods 0.000 claims abstract description 30
- 238000001694 spray drying Methods 0.000 claims abstract description 24
- 229910052742 iron Inorganic materials 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000003125 aqueous solvent Substances 0.000 claims abstract description 16
- 238000005406 washing Methods 0.000 claims abstract description 16
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims abstract description 14
- 229910052808 lithium carbonate Inorganic materials 0.000 claims abstract description 14
- 239000013589 supplement Substances 0.000 claims abstract description 12
- 239000002904 solvent Substances 0.000 claims abstract description 11
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 5
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 45
- 239000002245 particle Substances 0.000 claims description 30
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 16
- -1 ketone compounds Chemical class 0.000 claims description 14
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 13
- 239000011737 fluorine Substances 0.000 claims description 13
- 229910052731 fluorine Inorganic materials 0.000 claims description 13
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 12
- 238000002844 melting Methods 0.000 claims description 12
- 230000008018 melting Effects 0.000 claims description 9
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 229910001416 lithium ion Inorganic materials 0.000 claims description 6
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 6
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims description 5
- 229910001947 lithium oxide Inorganic materials 0.000 claims description 5
- 229910021389 graphene Inorganic materials 0.000 claims description 4
- SHXXPRJOPFJRHA-UHFFFAOYSA-K iron(iii) fluoride Chemical compound F[Fe](F)F SHXXPRJOPFJRHA-UHFFFAOYSA-K 0.000 claims description 4
- 239000006229 carbon black Substances 0.000 claims description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 3
- 239000002041 carbon nanotube Substances 0.000 claims description 3
- 150000002430 hydrocarbons Chemical class 0.000 claims description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 2
- 230000001476 alcoholic effect Effects 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims description 2
- 235000014413 iron hydroxide Nutrition 0.000 claims description 2
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 claims description 2
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 claims description 2
- HPGPEWYJWRWDTP-UHFFFAOYSA-N lithium peroxide Chemical compound [Li+].[Li+].[O-][O-] HPGPEWYJWRWDTP-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 150000002900 organolithium compounds Chemical class 0.000 claims description 2
- 238000010298 pulverizing process Methods 0.000 claims description 2
- 150000005846 sugar alcohols Polymers 0.000 claims description 2
- 150000001298 alcohols Chemical class 0.000 claims 1
- 150000002170 ethers Chemical class 0.000 claims 1
- 230000001502 supplementing effect Effects 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 8
- 239000002243 precursor Substances 0.000 abstract description 6
- 239000003513 alkali Substances 0.000 abstract description 4
- QSNQXZYQEIKDPU-UHFFFAOYSA-N [Li].[Fe] Chemical compound [Li].[Fe] QSNQXZYQEIKDPU-UHFFFAOYSA-N 0.000 abstract description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 21
- 239000012299 nitrogen atmosphere Substances 0.000 description 19
- 239000011248 coating agent Substances 0.000 description 10
- 238000000576 coating method Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 238000001816 cooling Methods 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- 235000019441 ethanol Nutrition 0.000 description 8
- 238000001914 filtration Methods 0.000 description 8
- 239000002002 slurry Substances 0.000 description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 6
- 229910018068 Li 2 O Inorganic materials 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000007580 dry-mixing Methods 0.000 description 3
- 239000012467 final product Substances 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 229910010586 LiFeO 2 Inorganic materials 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- 238000007740 vapor deposition Methods 0.000 description 2
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- 229910013553 LiNO Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000006256 anode slurry Substances 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 150000008365 aromatic ketones Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- RXKJFZQQPQGTFL-UHFFFAOYSA-N dihydroxyacetone Chemical compound OCC(=O)CO RXKJFZQQPQGTFL-UHFFFAOYSA-N 0.000 description 1
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 150000002642 lithium compounds Chemical class 0.000 description 1
- CASZBAVUIZZLOB-UHFFFAOYSA-N lithium iron(2+) oxygen(2-) Chemical compound [O-2].[Fe+2].[Li+] CASZBAVUIZZLOB-UHFFFAOYSA-N 0.000 description 1
- HQRPHMAXFVUBJX-UHFFFAOYSA-M lithium;hydrogen carbonate Chemical compound [Li+].OC([O-])=O HQRPHMAXFVUBJX-UHFFFAOYSA-M 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Images
Classifications
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- 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 relates to the technical field of lithium supplement agents, and particularly relates to a preparation method and application of a carbon-coated lithium ferrite material. The preparation method of the carbon-coated lithium ferrate material comprises the following steps of: sequentially carrying out first grinding, first spray drying, first sintering and first crushing on a mixture containing an iron source, a lithium source and a non-aqueous solvent to obtain a lithium ferrite material; and washing the lithium ferrite material by using an alcohol solvent, mixing the washed lithium ferrite material with an inorganic carbon source and the non-aqueous solvent, and sequentially carrying out second grinding, second spray drying and second sintering to obtain the carbon-coated lithium ferrite material. According to the invention, a twice sintering process is adopted, the precursor does not contain carbon during the first sintering, the generation of lithium carbonate and elementary substance iron is avoided, a lithium source which is not completely reacted is removed through washing, the residual alkali is reduced, and the prepared carbon-coated lithium iron material has high purity and high charging specific capacity.
Description
Technical Field
The invention relates to the technical field of lithium supplement agents, and particularly relates to a preparation method and application of a carbon-coated lithium ferrite material.
Background
The lithium ferrite is used for lithium supplement of the anode of the lithium ion battery, and a small amount of high-capacity lithium supplement additive is added in the anode slurry stirring process, so that the safety risk and the cost increase risk existing in lithium supplement at the cathode end can be avoided.
However, the existing preparation method of lithium iron serving as a lithium supplement agent has the defects of high energy consumption, low purity, complex flow, high cost, long period and the like.
For example, CN110498449a discloses a lithium ferrite material and a preparation method thereof, wherein an iron source, a lithium source, a carbon source and deionized water are mixed and ground, and spray-dried and sintered to obtain a lithium ferrite with a carbon-coated surface. However, CN110498449a has the following problems: the iron source and the carbon source used can generate C, CO and CO during calcination 2 Etc., wherein C, CO reduces the iron source to elemental iron, CO 2 The lithium carbonate can react with a lithium source and strongly basic lithium ferrite to generate lithium carbonate, so that the final product inevitably contains lithium carbonate, simple substance iron and the like, the purity is not high, and the specific charge capacity of the final product is low. In addition, the calcination temperature is high (650-1000 ℃), the time is long (24-48 h), the energy consumption is large, and the cost is high.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The first purpose of the invention is to provide a preparation method of a carbon-coated lithium ferrite material, which adopts a twice sintering process, wherein a precursor during the first sintering does not contain carbon, so that the generation of lithium carbonate and simple substance iron is avoided, and the prepared carbon-coated lithium ferrite material has high purity and high charging specific capacity.
The second object of the present invention is to provide a lithium replenishing agent.
A third object of the present invention is to provide a lithium ion battery.
In order to achieve the above purpose of the present invention, the following technical solutions are adopted:
in a first aspect, the invention provides a method for preparing a carbon-coated lithium ferrite material, which comprises the following steps:
and sequentially carrying out first grinding and first spray drying on the mixture containing the iron source, the lithium source and the non-aqueous solvent to obtain a precursor, then carrying out first sintering on the precursor, and then carrying out first crushing to obtain the lithium ferrite material.
And washing the lithium ferrite material by using an alcohol solvent, mixing the washed lithium ferrite material with an inorganic carbon source and a non-aqueous solvent, sequentially carrying out second grinding and second spray drying to fully wrap the inorganic carbon source on the outer surface of the lithium ferrite material, and then carrying out second sintering to obtain the carbon-coated lithium ferrite material.
The carbon-coated lithium ferrite material comprises a lithium ferrite material and a carbon coating layer coated on the surface of the lithium ferrite material.
The invention adopts the twice sintering process, the precursor does not contain carbon during the first sintering, the generation of lithium carbonate and simple substance iron is avoided, and the prepared lithium ferrite has high purity and high charging specific capacity; and carbon coating is carried out during the second sintering, so that excessive particle agglomeration is avoided, the conductivity of the material is increased, the residual alkali is reduced, and the processing performance is excellent.
Through carrying out first grinding and second grinding, grind the material granularity and diminish, make the material fully contact, both accelerated reaction rate, shortened reaction time, avoided the reaction incomplete again.
And the carbon coating is carried out by a second grinding and second spray drying mode, so that a carbon source and the first sintered lithium ferrite material can be fully mixed, and compared with a vapor deposition mode, the carbon coating cost is lower and the coating effect is better.
Residual lithium is removed by washing the lithium ferrite after the first sintering with a non-aqueous solvent, and free lithium (residual alkali) is greatly reduced.
In some embodiments of the present invention, the organic solvent that does not react with lithium ferrite is used for washing, and in order to ensure the washing effect and reduce the cost, the organic solvent should be capable of dissolving a certain amount of residual lithium such as lithium oxide, lithium hydroxide, lithium carbonate, and lithium bicarbonate. If the solubility is too low, the washing effect is not obtained.
In some embodiments of the present invention, the lithium ferrite material is further subjected to a filtration step after being washed with the alcohol solvent and before being mixed with the inorganic carbon source and the non-aqueous solvent.
By performing the second sintering, the solvent therein, lithium hydroxide generated during the processing, and the like can be sufficiently removed.
By using inorganic carbon sources, the production of CO can be avoided 2 Resulting in the presence of a lithium carbonate heterophasic phase in the final product. And the inorganic carbon source is added after the lithium ferrite material is prepared, so that the inorganic carbon source and the iron source can be prevented from reacting to generate an iron simple substance.
In some specific embodiments of the present invention, the carbon-coated lithium iron oxide material is used as a lithium supplement agent for lithium supplement of a positive electrode of a lithium ion battery.
Preferably, the mixture containing the iron source, the lithium source and the non-aqueous solvent further comprises a fluorine source.
When a fluorine source is included in the mixture, the lithium ferrite material is fluorine-doped (lithium-rich) lithium ferrite having the chemical formula Li 5 FeO 4-x/2 F x . Wherein, 0<x<0.5, including but not limited to any one of 0.1, 0.2, 0.3, 0.4, or a range of values therebetween.
When the mixture does not contain a fluorine source, the lithium ferrite material is lithium-rich lithium ferrite with a chemical formula of Li 5 FeO 4 。
The invention leads the material structure to be more stable and reduces the alkalinity of the lithium ferrite by doping fluorine.
In particular, due to F - Electric negative ratio O 2- Large and small amount of F dopedHetero, occupying the position of O, which attracts Fe, biasing Fe toward F, thereby increasing Li + The activity and ionic conductivity of the catalyst reduce the proportion of Li which is not completely reacted, the gram capacity of the catalyst is improved, and the alkalinity of the catalyst is obviously reduced.
Preferably, the fluorine source comprises at least one of lithium fluoride, iron fluoride and hydrogen fluoride.
Preferably, the molar ratio of the lithium element in the lithium source, the iron element in the iron source, and the fluorine element in the fluorine source is 5 to 5.5 (including but not limited to the point of any one of 5.1, 5.2, 5.3, 5.4 or a range between any two): 1:0 to 0.5 (including but not limited to any one of 0.1, 0.2, 0.3, 0.4 or a range between any two). More preferably 5 to 5.5:1:0.01 to 0.5.
Preferably, the iron source comprises at least one of iron oxide, iron nitrate, iron hydroxide and iron fluoride.
Preferably, the lithium source comprises a mixture of two of a low melting point lithium source and a high melting point lithium source. Wherein, the low-melting point lithium source refers to a lithium source which can be melted during sintering; a high melting point lithium source refers to a lithium source that does not melt upon sintering.
More preferably, the low-melting point lithium source includes at least one of lithium hydroxide, lithium carbonate, lithium nitrate, and an organic lithium compound, and the high-melting point lithium source includes at least one of lithium oxide, lithium peroxide, and lithium fluoride.
Preferably, the percentage of the molar amount of lithium element in the low melting point lithium source to the molar amount of total lithium element in the lithium source is ≦ 25%, including but not limited to the point value of any one of 23%, 20%, 15%, 10%, 5%, 1%, or a range value between any two. This avoids erosion of the saggar.
In some embodiments of the invention, the organolithium compound comprises at least one of lithium oxalate, lithium carboxylate and alkyl lithium.
In an inert gas atmosphere, lithium carbonate alone is used, and the lithium carbonate is not completely decomposed, so that lithium ferrite cannot be prepared. When lithium oxide is used alone as a lithium source, lithium ferrite can be prepared, but because lithium oxide has a high melting point, lithium ferrite does not melt during sintering, diffusion between solids is slow, and reaction time is long.
According to the invention, the low-melting-point lithium source and the high-melting-point lithium source are adopted at the same time, and the proportion of the low-melting-point lithium source and the high-melting-point lithium source is controlled, so that the reaction time can be shortened, and the sagger can be prevented from being corroded by excessive strong-alkaline molten-state lithium source.
Preferably, the temperature of the first sintering is 600 to 850 ℃, including but not limited to the values of any one of 650 ℃, 700 ℃, 750 ℃, 800 ℃ or the range values between any two.
The holding time of the first sintering is 5-24 h, including but not limited to any one of the point values of 7h, 9h, 10h, 12h, 15h, 18h, 20h and 22h or the range value between any two.
Preferably, the inorganic carbon source includes at least one of graphite, graphene, carbon nanotubes, and carbon black.
More preferably, the carbon black comprises conductive carbon black.
Preferably, the mass of the inorganic carbon source is 1% to 5% of the mass of the lithium ferrite material, including but not limited to the point of any one of 2%, 3%, 4%, or the range between any two.
Preferably, the temperature of the second sintering is 400 to 850 ℃, including but not limited to any one of the points of 450 ℃, 500 ℃, 550 ℃, 600 ℃, 650 ℃, 700 ℃, 750 ℃, 800 ℃ or a range between any two.
The holding time of the second sintering is 2-10 h, including but not limited to any one of 3h, 5h, 6h, 7h, 8h and 9h or a range between any two.
Preferably, the mass fraction of water in the non-aqueous solvent is ≦ 0.05%, including but not limited to the values of any one of 0.04%, 0.03%, 0.02%, 0.01% or ranges between any two.
The non-aqueous solvent is adopted to disperse the ground material, so that the reaction of the raw material and the lithium ferrite material generated in the first step with water is avoided.
Preferably, the non-aqueous solvent used for the first grinding and the second grinding includes at least one of an alcohol compound, an ether compound, a hydrocarbon compound, and a ketone compound.
For example, the alcohol compound includes, but is not limited to, absolute ethanol, methanol, propanol, isopropanol, and the like. The ether compound includes methyl ether, ethyl ether, butyl ether, etc., but is not limited thereto. The hydrocarbon compound includes alkane, alkene, aromatic hydrocarbon, halogenated hydrocarbon, etc., but is not limited thereto. The ketone compound includes aliphatic ketone, alicyclic ketone, aromatic ketone, saturated ketone, unsaturated ketone, etc., but is not limited thereto.
Preferably, the alcoholic solvent used for the washing includes at least one of monohydric alcohol, dihydric alcohol and polyhydric alcohol, such as methanol, ethanol, isopropanol, propanol, ethylene glycol, propylene glycol, and the like, but is not limited thereto.
Preferably, the first grinding and/or the second grinding comprise sanding.
Through carrying out the sanding twice, grind the material granularity and diminish, make the material intensive mixing, both accelerated reaction rate, avoided the reaction incomplete again.
Preferably, the first grinding is carried out until the D50 particle size of the material is 200-400 nm; including but not limited to values at any one of 220nm, 250nm, 280nm, 300nm, 330nm, 350nm, 380nm, or ranges between any two.
Preferably, the second grind is to a D50 particle size of the material of 100 to 300nm, including but not limited to values of any one of 120nm, 150nm, 180nm, 200nm, 230nm, 250nm, 280nm, or ranges between any two.
In some preferred embodiments of the invention, the D50 particle size of the first spray-dried material is from 4 to 8 μm; including but not limited to a point value of any one of 5 μm, 6 μm, 7 μm, or a range value between any two.
In some preferred embodiments of the invention, the first comminuted material has a D50 particle size of from 5 to 12 μm; including but not limited to a point value of any one of 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, 11 μm, or a range value between any two.
Preferably, after the second sintering, a step of performing second pulverization is further included.
In some preferred embodiments of the invention, the D50 particle size of the second comminuted material is 1 to 3 μm, including but not limited to values at any one of 1.5 μm, 2 μm, 2.5 μm or ranges between any two.
In some embodiments of the invention, the first sintering and/or the second sintering are performed under an inert atmosphere to avoid the formation of a heterogeneous phase.
Preferably, the inert atmosphere comprises a nitrogen atmosphere and/or an argon atmosphere.
In some specific embodiments of the present invention, a process flow diagram of a method for preparing a carbon-coated lithium ferrate material is shown in fig. 1. In some embodiments of the present invention, the lithium ferrite material is further subjected to a filtration step after being washed with an alcohol solvent. The filter cake obtained after washing and filtration is used directly for carbon coating in admixture with an inorganic carbon source and a non-aqueous solvent. The filtrate obtained after washing and filtration can be evaporated to obtain a residue and a solvent, respectively, wherein the residue can be used for extracting lithium, and the solvent can be recycled after removing water.
In a second aspect, the invention provides a lithium supplement agent, which comprises the carbon-coated lithium ferrite material prepared by the preparation method of the carbon-coated lithium ferrite material.
In a third aspect, the invention provides a lithium ion battery, which comprises the lithium supplement agent.
Compared with the prior art, the invention has the beneficial effects that:
(1) According to the preparation method of the carbon-coated lithium ferrite material, provided by the invention, a twice sintering process is adopted, the precursor does not contain carbon during the first sintering, the generation of lithium carbonate and simple substance iron is avoided, and the prepared lithium ferrite has high purity and high charging specific capacity; and carbon coating is carried out during the second sintering, so that excessive particle agglomeration is avoided, the conductivity of the material is increased, the residual alkali is reduced, and the processing performance is excellent.
(2) According to the preparation method of the carbon-coated lithium ferrite material, provided by the invention, the first grinding and the second grinding are carried out, so that the granularity of the material is reduced, the material is fully contacted, the reaction rate is increased, the reaction time is shortened, and incomplete reaction is avoided.
(3) According to the preparation method of the carbon-coated lithium ferrite material, provided by the invention, carbon coating is carried out in a second grinding and second spray drying mode, so that a carbon source and the first sintered lithium ferrite material can be fully mixed, and compared with a vapor deposition mode, the carbon coating cost is lower and the coating effect is better.
(4) According to the preparation method of the carbon-coated lithium ferrite material, provided by the invention, the material structure is more stable by doping fluorine, and the alkalinity of lithium ferrite is reduced.
(5) According to the preparation method of the carbon-coated lithium ferrite material, at least two lithium sources are adopted, so that excessive corrosion to the saggar is avoided, and the activity of the material is increased.
(6) According to the preparation method of the carbon-coated lithium ferrite material, provided by the invention, the materials are dispersed and ground by adopting the organic solvent, so that the reaction of the raw materials and the lithium ferrite material generated in the first step of reaction with water is avoided.
(7) According to the preparation method of the carbon-coated lithium ferrite material, provided by the invention, the lithium ferrite material after primary crushing is washed by adopting the non-aqueous solvent, so that unreacted lithium can be washed completely, and the alkalinity of the lithium ferrite is greatly reduced.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
Fig. 1 is a process flow diagram of a method for preparing a carbon-coated lithium ferrite material according to the present invention;
FIG. 2 is an XRD pattern of a lithium ferrite material prepared in example 1;
FIG. 3 is an XRD pattern of the lithium ferrite material prepared in example 6.
Detailed Description
The technical solutions of the present invention will be clearly and completely described below in conjunction with the accompanying drawings and the detailed description, but those skilled in the art will understand that the following described embodiments are a part of the embodiments of the present invention, rather than all of the embodiments, and are only used for illustrating the present invention, and should not be construed as limiting the scope of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention. The examples, in which specific conditions are not specified, were carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The process flow diagram of the preparation method of the carbon-coated lithium ferrite material provided by the invention is shown in figure 1.
Example 1
The preparation method of the carbon-coated lithium ferrite material provided by the embodiment comprises the following steps:
(1) 0.995mol Fe 2 O 3 ，6.7mol LiOH，2mol Li 2 O and 0.01mol of FeF 3 (i.e., the molar ratio of Li element: fe element: F element is 5.35:1, and the molar amount of lithium element in lithium hydroxide is 62.6% based on the molar amount of the total lithium elements in the lithium source), 1500ml of anhydrous ethanol was added, and this was subjected to sand grinding (i.e., first grinding) to obtain a slurry having a particle size D50 of 320nm. And (3) spray-drying the obtained slurry in a nitrogen atmosphere (namely, carrying out first spray-drying), keeping the temperature of the dried material (D50 with the particle size of 5.642 mu m) at 700 ℃ for 12h in the nitrogen atmosphere (namely, carrying out first sintering), cooling to room temperature, taking out and crushing to obtain the lithium ferrite material with the D50 particle size of 7.458 mu m, wherein the lithium ferrite material is fluorine-doped lithium ferrite.
Then adding the prepared lithium ferrite material into a beaker filled with 1500ml of glycol, sealing, stirring for 30min, then filtering by using a polytetrafluoroethylene microporous filter membrane, and washing by using glycol until the conductivity reaches 500us/cm.
(2) Adding 309.19g of the lithium ferrite material washed in the step (1) and 6.31g of conductive carbon black (namely the mass of the inorganic carbon source is 2.04 percent of the mass of the lithium ferrite material) into 1000ml of absolute ethyl alcohol, sanding again (namely carrying out second grinding until the D50 particle size is 150 nm), then carrying out spray drying (namely carrying out second spray drying) in a nitrogen atmosphere, then carrying out heat preservation for 8h at 500 ℃ in the nitrogen atmosphere (namely carrying out second sintering), cooling to room temperature, and then crushing to obtain the carbon-coated lithium ferrite material with the D50 particle size of 1.722 mu m.
Example 2
The preparation method of the carbon-coated lithium ferrite material provided by the embodiment comprises the following steps:
(1) 2mol of Fe (OH) 3 ，2mol LiOH，4mol Li 2 O and 1mol LiF (i.e., a molar ratio of Li element: fe element: F element of 5.5. And (3) spray-drying the obtained slurry in a nitrogen atmosphere (namely, carrying out first spray-drying), keeping the temperature of the dried material (D50 with the particle size of 5.486 mu m) at 600 ℃ for 24h in the nitrogen atmosphere (namely, carrying out first sintering), cooling to room temperature, taking out and crushing to obtain the lithium ferrite material with the D50 particle size of 7.639 mu m, which is fluorine-doped lithium ferrite.
Then adding the prepared lithium ferrite material into a beaker filled with 1500ml of glycol, sealing, stirring for 30min, then filtering by using a polytetrafluoroethylene microporous filter membrane, and washing by using glycol until the conductivity reaches 500us/cm.
(2) Adding 302.94g of the lithium ferrite material and 3.06g of graphene (namely the mass of the inorganic carbon source is 1.01% of the mass of the lithium ferrite material) which are washed in the step (1) into 1000ml of isopropanol, sanding again (namely, carrying out second grinding until the D50 particle size is 100 nm), then carrying out spray drying (namely, carrying out second spray drying) in a nitrogen atmosphere, then carrying out heat preservation for 2h at 800 ℃ in the nitrogen atmosphere (namely, carrying out second sintering), cooling to room temperature, and then crushing to obtain the carbon-coated lithium ferrite material with the D50 particle size of 2.455 mu m.
Example 3
The preparation method of the carbon-coated lithium ferrite material provided by the embodiment comprises the following steps:
(1) Mixing 1mol of Fe 2 O 3 ，1mol LiOH，4mol Li 2 O and 0.5mol Li 2 CO 3 (i.e., the molar ratio of Li element: fe element is 5:1, and the molar amount of lithium element in lithium hydroxide and lithium carbonate is 20% of the total molar amount of lithium element in the lithium source), 1500ml of absolute ethanol was added and sand ground (i.e., first grinding) to obtain a slurry having a particle size D50 of 360nm. And (3) spray-drying the obtained slurry in a nitrogen atmosphere (namely, carrying out first spray-drying), keeping the temperature of the dried material (D50 with the particle size of 8.254 mu m) at 850 ℃ for 5h in the nitrogen atmosphere (namely, carrying out first sintering), cooling to room temperature, taking out and crushing to obtain the lithium ferrite material with the D50 particle size of 9.178 mu m, wherein the lithium ferrite material is lithium ferrite.
Then adding the prepared lithium ferrite material into a beaker filled with 1500ml of ethylene glycol, sealing, stirring for 30min, then filtering by using a polytetrafluoroethylene microporous filter membrane, and washing by using the ethylene glycol until the conductivity is 500us/cm.
(2) Adding 309.19g of the lithium ferrite material and 6.31g of graphite powder (namely the mass of the inorganic carbon source is 2.04 percent of the mass of the lithium ferrite material) which are washed in the step (1) into 1000ml of absolute ethyl alcohol, sanding again (namely, carrying out second grinding until the D50 particle size is 300 nm), then carrying out spray drying (namely, carrying out second spray drying) in a nitrogen atmosphere, then carrying out heat preservation for 6h at 600 ℃ in the nitrogen atmosphere (namely, carrying out second sintering), cooling to room temperature and then crushing to obtain the carbon-coated lithium ferrite material with the D50 particle size of 2.096 mu m.
Example 4
The preparation method of the carbon-coated lithium ferrite material provided by the embodiment comprises the following steps:
(1) 2mol of Fe (NO) 3 ) 3 ，4mol LiNO 3 ，3mol Li 2 O and 0.2mol of LiF (i.e., a molar ratio of Li element: fe element: F element of 5.1The molar amount of lithium element in the lithium nitrate, which was 39.2% of the molar amount of the total lithium elements in the lithium source, was added to 1500ml of carbon tetrachloride, which was sanded (i.e., first milled) to obtain a slurry having a particle size D50 of 300nm. And (3) spray-drying the obtained slurry in a nitrogen atmosphere (namely, carrying out first spray-drying), keeping the temperature of the dried material (D50 with the particle size of 5.318 mu m) at 700 ℃ for 12h in the nitrogen atmosphere (namely, carrying out first sintering), cooling to room temperature, taking out and crushing to obtain the lithium ferrite material with the D50 particle size of 11.907 mu m, wherein the lithium ferrite material is fluorine-doped lithium ferrite.
Then adding the prepared lithium ferrite material into a beaker filled with 1500ml of glycol, sealing, stirring for 30min, then filtering by using a polytetrafluoroethylene microporous filter membrane, and washing by using glycol until the conductivity reaches 500us/cm.
(2) Adding 309.11g and 9.00g of the carbon nano tube (namely the mass of the inorganic carbon source is 2.91 percent of the mass of the lithium ferrite material) washed in the step (1) into 1000ml of carbon tetrachloride, sanding again (namely, carrying out second grinding until the D50 particle size is 240 nm), then carrying out spray drying (namely, carrying out second spray drying) in a nitrogen atmosphere, keeping the temperature at 400 ℃ for 10h (namely, carrying out second sintering) in the nitrogen atmosphere, cooling to room temperature, and crushing to obtain the carbon-coated lithium ferrite material with the D50 particle size of 2.319 mu m.
Example 5
The preparation method of the carbon-coated lithium ferrate material provided in this example is substantially the same as that of example 1, except that 0.01mol of FeF is added 3 Replacement by 0.005mol Fe 2 O 3 . Namely, the molar ratio of each element Li: fe: f =5.35:1:0.
example 6
The preparation method of the carbon-coated lithium ferrate material provided in this example is substantially the same as that of example 1, except that 6.7mol of LiOH and 2mol of Li are added 2 O was replaced with 10.7mol of LiOH. That is, lithium hydroxide alone is used as a lithium source.
Comparative example 1
This comparative example provides a lithium ferrite material prepared in substantially the same manner as in example 1 except that the lithium ferrite material obtained in step (1) was not washed.
Comparative example 2
The preparation method of the carbon-coated lithium ferrite material provided by the comparative example adopts a dry mixing method, and specifically comprises the following steps:
0.995mol Fe 2 O 3 ，6.7mol LiOH，2mol Li 2 O and 0.01mol of FeF 3 Adding into a slant mixer, adding grinding medium balls for dry mixing for 2.5h, and then keeping the temperature at 700 ℃ for 12h under nitrogen atmosphere. Cooling to room temperature, taking out and crushing, adding the crushed material and 6.31g of conductive carbon black into an inclined mixer, adding grinding medium balls into the inclined mixer for dry mixing for 2.5 hours, keeping the temperature of the mixture at 500 ℃ for 8 hours under the nitrogen atmosphere, cooling to room temperature, and crushing to obtain the carbon-coated lithium ferrite material.
Comparative example 3
The preparation method of the lithium ferrite material provided by the comparative example is basically the same as that of the example 2, except that no graphene is added in the step (2). I.e. no carbon coating. The lithium ferrite material provided by the comparative example is fluorine-doped lithium ferrite.
Examples of the experiments
The D50 particle size and basicity of the carbon-coated lithium ferrite materials prepared in the above examples, the lithium ferrite materials prepared in comparative examples 1 and 3, and the carbon-coated lithium ferrite material prepared in comparative example 2 were measured, respectively, and assembled into a lithium ion battery as a positive electrode lithium supplement agent, and then the electrochemical properties thereof were tested, and the results are shown in table 1 below.
It can be seen from the comparison of the experimental data of example 1 and example 5 that the basicity of the lithium ferrite material is reduced by doping fluorine in example 1, and the material structure is more stable and the electrochemical performance is more excellent.
Comparing comparative example 1 with example 1, it can be seen that the alkalinity of the prepared material is obviously reduced after the washing is increased in example 1, and the electrical property of the material is not greatly influenced.
As can be seen by comparing example 1 with example 6, in example 6, lithium hydroxide alone is used as a lithium source, and the prepared material has high alkalinity and is easy to absorb water to generate LiFeO 2 A heterogeneous phase; and in the primary sintering, the lithium hydroxide melts and then the solution corrodes the sagger of the material. In the embodiment 1, the proportion of lithium hydroxide is reduced by using the composite lithium source, so that the corrosion to the sagger is reduced, the alkalinity is reduced, and the water is not easy to absorb to generate LiFeO 2 And (4) miscellaneous phase.
Wherein, as shown in FIG. 2, the XRD pattern of the lithium ferrite material prepared in example 1 is shown; FIG. 3 shows the XRD pattern of the lithium ferrite material prepared in example 6. As can be seen by comparing fig. 2 and 3, in example 6, lithium hydroxide alone was used as a lithium source, and a hetero-peak was generated.
While particular embodiments of the present invention have been illustrated and described, it will be appreciated that the above embodiments are only intended to illustrate the technical solution of the present invention and not to limit it; those of ordinary skill in the art will understand that: modifications may be made to the above-described embodiments, or equivalents may be substituted for some or all of the features thereof without departing from the spirit and scope of the present invention; the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention; it is therefore intended to cover in the appended claims all such changes and modifications that are within the scope of this invention.
Claims (10)
1. A preparation method of a carbon-coated lithium ferrate material is characterized by comprising the following steps of:
sequentially carrying out first grinding, first spray drying, first sintering and first crushing on a mixture containing an iron source, a lithium source and a non-aqueous solvent to obtain a lithium ferrite material;
and washing the lithium ferrite material by using an alcohol solvent, mixing the washed lithium ferrite material with an inorganic carbon source and the non-aqueous solvent, and sequentially carrying out second grinding, second spray drying and second sintering to obtain the carbon-coated lithium ferrite material.
2. The method according to claim 1, wherein the mixture containing the iron source, the lithium source, and the non-aqueous solvent further includes a fluorine source;
preferably, the fluorine source comprises at least one of lithium fluoride, iron fluoride and hydrogen fluoride;
preferably, the molar ratio of the lithium element in the lithium source, the iron element in the iron source and the fluorine element in the fluorine source is 5 to 5.5:1:0 to 0.5.
3. The method of preparing a carbon-coated lithium ferrate material of claim 1, wherein the iron source comprises at least one of iron oxide, iron nitrate, iron hydroxide, and iron fluoride;
preferably, the lithium source comprises a low melting point lithium source and a high melting point lithium source; more preferably, the low melting point lithium source includes at least one of lithium hydroxide, lithium carbonate, lithium nitrate, and an organolithium compound, and the high melting point lithium source includes at least one of lithium oxide, lithium peroxide, and lithium fluoride;
preferably, the percentage of the molar amount of lithium element in the low-melting-point lithium source to the molar amount of the total lithium element in the lithium source is less than or equal to 25%.
4. The method according to claim 1, wherein the first sintering temperature is 600-850 ℃ and the holding time is 5-24 h.
5. The method of preparing a carbon-coated lithium ferrite material according to claim 1, wherein the inorganic carbon source comprises at least one of graphite, graphene, carbon nanotubes, and carbon black;
preferably, the mass of the inorganic carbon source is 1-5% of the mass of the lithium ferrite material.
6. The method according to claim 1, wherein the second sintering temperature is 400-850 ℃ and the holding time is 2-10 h.
7. The method according to claim 1, wherein the mass fraction of water in the nonaqueous solvent is less than or equal to 0.05%; preferably, the non-aqueous solvent includes at least one of alcohol compounds, ether compounds, hydrocarbon compounds and ketone compounds;
preferably, the alcoholic solvent includes at least one of monohydric alcohol, dihydric alcohol and polyhydric alcohol.
8. The method of preparing a carbon-coated lithium ferrate material of claim 1, wherein the first grinding and/or the second grinding comprises sanding;
preferably, the first grinding is carried out until the D50 particle size of the material is 200-400 nm;
preferably, the second grinding is carried out until the D50 particle size of the material is 100-300 nm;
preferably, after the second sintering, a step of performing a second pulverization is further included.
9. A lithium supplementing agent comprising the carbon-coated lithium ferrite material produced by the method for producing a carbon-coated lithium ferrite material according to any one of claims 1 to 8.
10. A lithium ion battery comprising the lithium supplement agent according to claim 9.
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