CN115719808B - Preparation method and application of lithium ferrite lithium supplementing agent - Google Patents
Preparation method and application of lithium ferrite lithium supplementing agent Download PDFInfo
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- CN115719808B CN115719808B CN202211580174.0A CN202211580174A CN115719808B CN 115719808 B CN115719808 B CN 115719808B CN 202211580174 A CN202211580174 A CN 202211580174A CN 115719808 B CN115719808 B CN 115719808B
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- ferrite
- supplementing agent
- mixed material
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- JXGGISJJMPYXGJ-UHFFFAOYSA-N lithium;oxido(oxo)iron Chemical compound [Li+].[O-][Fe]=O JXGGISJJMPYXGJ-UHFFFAOYSA-N 0.000 title claims abstract description 89
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 82
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 82
- 230000001502 supplementing effect Effects 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 54
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 51
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 41
- 239000000463 material Substances 0.000 claims abstract description 40
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000000227 grinding Methods 0.000 claims abstract description 24
- 238000005245 sintering Methods 0.000 claims abstract description 23
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000000314 lubricant Substances 0.000 claims abstract description 12
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000011247 coating layer Substances 0.000 claims abstract description 9
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 25
- 239000013589 supplement Substances 0.000 claims description 21
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 18
- 238000000498 ball milling Methods 0.000 claims description 13
- 239000002245 particle Substances 0.000 claims description 12
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 6
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 5
- 239000002041 carbon nanotube Substances 0.000 claims description 5
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 claims description 4
- 239000004354 Hydroxyethyl cellulose Substances 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- 229910021389 graphene Inorganic materials 0.000 claims description 4
- 229910002804 graphite Inorganic materials 0.000 claims description 4
- 239000010439 graphite Substances 0.000 claims description 4
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 3
- 229920002472 Starch Polymers 0.000 claims description 3
- 229910003481 amorphous carbon Inorganic materials 0.000 claims description 3
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 3
- ZPJGNHUPXGDASP-UHFFFAOYSA-L dilithium;hexanedioate Chemical compound [Li+].[Li+].[O-]C(=O)CCCCC([O-])=O ZPJGNHUPXGDASP-UHFFFAOYSA-L 0.000 claims description 3
- 239000008103 glucose Substances 0.000 claims description 3
- 229920003063 hydroxymethyl cellulose Polymers 0.000 claims description 3
- 229940031574 hydroxymethyl cellulose Drugs 0.000 claims description 3
- 239000011301 petroleum pitch Substances 0.000 claims description 3
- 238000004321 preservation Methods 0.000 claims description 3
- 239000008107 starch Substances 0.000 claims description 3
- 235000019698 starch Nutrition 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000003912 environmental pollution Methods 0.000 abstract description 5
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 7
- 229920000604 Polyethylene Glycol 200 Polymers 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000001816 cooling Methods 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 238000007599 discharging Methods 0.000 description 3
- 238000003801 milling Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 229920002593 Polyethylene Glycol 800 Polymers 0.000 description 1
- 238000001467 acupuncture Methods 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- -1 lithium hexafluorophosphate Chemical compound 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 125000001979 organolithium group Chemical group 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229920002523 polyethylene Glycol 1000 Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
Classifications
-
- 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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- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to the technical field of lithium ion batteries, in particular to a preparation method and application of a lithium ferrite lithium supplementing agent. The preparation method of the lithium ferrite lithium supplementing agent comprises the following steps: mixing a carbon source, ferric oxide and an organic lubricant, and performing first grinding to obtain a first mixed material; the first mixed material is mixed with an organic lithium source and subjected to second grinding, so that a second mixed material is obtained; sintering the second mixed material to obtain the lithium ferrite lithium supplementing agent; the lithium ferrite lithium supplementing agent comprises lithium ferrite and a carbon coating layer coated on the surface of the lithium ferrite. The preparation method has the advantages of short flow, low synthesis cost, low energy consumption, low material loss, low environmental pollution and the like.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a preparation method and application of a lithium ferrite lithium supplementing agent.
Background
Compared with other batteries, the lithium battery has the characteristics of high energy density, smaller packaging size and quality, no influence of memory effect, lower self-discharge rate, safe use, relatively stable charge and discharge, strong environment adaptation and the like. Lithium batteries have become one of the hot spots in industry development in recent years.
In the charging and discharging process of the lithium ion battery, lithium used for anode and cathode migration in the battery is reduced due to the reasons that active lithium is lost in the first charging and discharging process, lithium dendrite is formed by lithium ions, lithium is dissolved in electrolyte in the charging and discharging process, and the like, so that the electrical performance of the battery is rapidly reduced, and the using effect is affected. The lithium supplementing agent can supplement the gaps of lithium acupuncture points caused by discharge, ensure the electrical performance index of the battery and ensure the charge and discharge efficiency of the battery.
However, the preparation method of the lithium supplementing agent in the prior art often adopts an in-situ coating method, and the method has the defects of long process flow, complex operation, high preparation cost and the like.
In addition, the prior art adopts organic iron as an iron source, and has the defects of easy environmental pollution, high cost and the like.
In view of this, the present invention has been made.
Disclosure of Invention
The first aim of the invention is to provide a preparation method of a lithium ferrite lithium supplementing agent, which has the advantages of short flow, low synthesis cost, low energy consumption, low material loss, low environmental pollution and the like.
The second purpose of the invention is to provide the application of the lithium ferrite lithium supplement prepared by the preparation method of the lithium ferrite lithium supplement in a lithium ion battery.
In order to achieve the above object of the present invention, the following technical solutions are specifically adopted:
The invention provides a preparation method of a lithium ferrite lithium supplementing agent, which comprises the following steps:
Mixing a carbon source, ferric oxide and an organic lubricant, and performing first grinding to obtain a first mixed material; the first mixed material is mixed with an organic lithium source and subjected to second grinding, so that a second mixed material is obtained; sintering the second mixed material to obtain the lithium ferrite lithium supplementing agent;
The lithium ferrite lithium supplementing agent comprises lithium ferrite and a carbon coating layer coated on the surface of the lithium ferrite.
In the above technical solution, further, a ratio of a total mass of the carbon element in the carbon source and the organic lubricant to a mass of the iron element in the iron oxide is 9.62% to 12.13%.
In the above technical solution, further, the carbon source includes an inorganic carbon source and/or an organic carbon source;
preferably, the inorganic carbon source comprises at least one of carbon nanotubes, graphene, graphite, C 60, and amorphous carbon;
Preferably, the organic carbon source includes at least one of glucose, hydroxymethyl cellulose, soluble starch, hydroxyethyl cellulose, and petroleum pitch.
In the above technical solution, further, the organic lubricant includes polyethylene glycol.
In the above technical solution, further, the organic lithium source includes at least one of lithium acetate, lithium oxalate and lithium adipate.
In the above technical scheme, further, the molar ratio of the lithium element in the organic lithium source to the iron element in the iron oxide is 5.05-5.8: 1.
In the technical scheme, further, the particle size D 50 of the second mixed material is less than or equal to 15 mu m;
Preferably, the D 50 particle size of the lithium ferrite lithium supplementing agent is less than or equal to 15 mu m.
In the technical scheme, further, the sintering temperature is 700-800 ℃, and the sintering heat preservation time is 15-20 h.
In the above technical solution, further, the first grinding and/or the second grinding includes ball milling;
preferably, the time of the first grinding and/or the second grinding is 4-10 h.
The invention also provides an application of the lithium ferrite lithium supplement prepared by the preparation method of the lithium ferrite lithium supplement in a lithium ion battery.
Compared with the prior art, the invention has the beneficial effects that:
(1) The preparation method of the lithium ferrite lithium supplementing agent provided by the invention adopts a one-step sintering method to synthesize lithium ferrite, and has the advantages of short process flow, simplicity in operation, low preparation cost, low energy consumption, low material loss, low environmental pollution and the like.
(2) The lithium ferrite lithium supplementing agent prepared by the preparation method provided by the invention has excellent electrochemical performance.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are needed in the description of the embodiments or the prior art will be briefly described, and it is obvious that the drawings in the description below are some embodiments of the present invention, and other drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.
FIG. 1 is an XRD pattern of a lithium ferrite lithium-supplementing agent prepared in example 1 of the present invention;
FIG. 2 is a SEM image of the lithium ferrite lithium-supplementing agent of example 1 of the present invention at 1000 times magnification;
FIG. 3 is an SEM image of 10000 times of magnification of the lithium ferrite lithium-supplementing agent prepared in example 1 of the present invention.
Detailed Description
The technical solution of the present invention will be clearly and completely described below with reference to the accompanying drawings and detailed description, but it will be understood by those skilled in the art that the examples described below are some, but not all, examples of the present invention, and are intended to be illustrative of the present invention only and should not be construed as limiting the scope of the present invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
In a first aspect, the invention provides a method for preparing a lithium ferrite lithium supplementing agent, which comprises the following steps:
and mixing a carbon source, ferric oxide and an organic lubricant, and performing first grinding to obtain a first mixed material.
Wherein the organic lubricant also provides elemental carbon as a carbon source.
The carbon element and the iron element can be uniformly distributed by the first grinding.
And mixing the first mixed material with an organic lithium source, and performing second grinding to obtain a second mixed material.
The lithium element, the carbon element and the iron element can be uniformly distributed by the second grinding.
And sintering the second mixed material to obtain the lithium ferrite lithium supplementing agent.
In the sintering process, the organic lithium source reacts with the ferric oxide to generate lithium ferrite, and a uniform carbon coating layer is formed on the surface of the lithium ferrite.
The lithium ferrite lithium supplementing agent comprises lithium ferrite (lithium ferrite rich in lithium and having a chemical formula of Li 5FeO4) and a carbon coating layer coated on the surface of the lithium ferrite.
The preparation method of the lithium ferrite lithium supplementing agent provided by the invention synthesizes lithium ferrite by adopting specific raw materials and adopting a one-step sintering method, and has the advantages of short process flow, simplicity in operation, low preparation cost, low energy consumption, low material loss, low environmental pollution and the like.
And the alkalinity of the lithium ferrite lithium supplementing agent prepared by the one-step sintering method is equivalent to that of the lithium supplementing agent prepared by the two-step in-situ coating method.
Further, compared with the prior art that organic iron is adopted, the method adopts the ferric oxide as an iron source, so that the granularity of the ferric oxide is finer, the LFO forming is more uniform in the sintering process, the second mixed material D 50 is easier to reach the required granularity, the product source is wider, the price is lower, no pollution is caused, and the method is more suitable for preparing lithium ferrite.
Furthermore, the lithium ferrite lithium supplementing agent prepared by the preparation method provided by the invention has the advantages of more regular structural crystal form, more uniform formation, higher purity and more excellent electrochemical performance.
Preferably, the ratio of the total mass of carbon element (m Total (S) C) in the carbon source and the organic lubricant to the mass of iron element (m Fe) in the iron oxide is 9.62% to 12.13%, including but not limited to a point value of any one of 10%, 10.5%, 11%, 11.5%, 12%, or a range value between any two. I.e. m Total (S) C/mFe x 100% = 9.62% to 12.13%.
Preferably, the carbon source comprises an inorganic carbon source and/or an organic carbon source. The carbon source is used for providing carbon elements and can be coated on the surface of lithium ferrite after sintering.
Preferably, the inorganic carbon source includes at least one of carbon nanotubes, graphene, graphite, C 60, and amorphous carbon.
Preferably, the organic carbon source includes at least one of glucose, hydroxymethyl cellulose, soluble starch, hydroxyethyl cellulose, and petroleum pitch.
Preferably, the organic lubricant includes polyethylene glycol, such as at least one of PEG-800, PEG-1000, and PEG-1200, but is not limited thereto.
Wherein polyethylene glycol is used as both an organic lubricant and a carbon source.
Preferably, the organic lithium source comprises at least one of lithium acetate, lithium oxalate and lithium adipate.
Preferably, the molar ratio of the lithium element in the organolithium source to the iron element in the iron oxide is 5.05 to 5.8:1, including but not limited to a point value of any one of, or a range value between, 5.1:1, 5.15:1, 5.2:1, 5.3:1, 5.4:1, 5.5:1, 5.6:1, 5.7:1.
Preferably, the D 50 particle size of the second mixed material is less than or equal to 15 mu m; including but not limited to a dot value of any one of 15 μm, 13 μm, 11 μm, 10 μm, 8 μm, 6 μm, 5 μm, 3 μm, 1 μm, or a range value between any two.
Preferably, the D 50 particle size of the lithium ferrite lithium supplement is less than or equal to 15 μm, including but not limited to a dot value of any one of 15 μm, 13 μm, 11 μm, 10 μm, 8 μm,6 μm, 5 μm,3 μm, 1 μm or a range value between any two.
Preferably, the sintering temperature is 700-800 ℃, including but not limited to any one or range of values between 710 ℃, 720 ℃, 730 ℃, 740 ℃, 750 ℃, 760 ℃, 770 ℃, 780 ℃, 790 ℃.
The sintering heat preservation time is 15-20 h, including but not limited to any one of the point values of 16h, 17h, 18h and 19h or a range value between any two.
In some embodiments of the invention, the sintering temperature rise rate is 1 to 5 ℃/min, including but not limited to a point value of any one of 2 ℃/min, 3 ℃/min, 4 ℃/min, or a range value between any two.
In some embodiments of the invention, the sintering is performed in a tube furnace.
In some embodiments of the invention, after the sintering, a step of crushing is further included.
Preferably, the D 50 particle size of the crushed to lithium ferrite lithium supplement is less than or equal to 15 μm, including but not limited to a point value of any one of 15 μm, 13 μm, 11 μm, 10 μm, 8 μm, 6 μm, 5 μm, 3 μm, 1 μm or a range value between any two.
Preferably, the first grinding and/or the second grinding comprises ball milling. I.e. the first milling may be performed in a ball milling manner and the second milling may be performed in a ball milling manner.
Preferably, the time of the first grinding and/or the second grinding is 4-10 h, including but not limited to a point value of any one of 4.5h, 5h, 6h, 7h, 8h, 9h or a range value between any two.
In some embodiments of the invention, the first grinding and/or the second grinding is performed using a ball-and-pick milling process.
In a second aspect, the invention provides an application of the lithium ferrite lithium supplement prepared by the preparation method of the lithium ferrite lithium supplement in a lithium ion battery.
The lithium ferrite lithium supplementing agent prepared by the method can be used for supplementing lithium exhausted in the use process of the battery, guaranteeing balance of migration lithium and delaying the weakening rate of the battery.
Embodiments of the present invention will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
Example 1
The preparation method of the lithium ferrite lithium supplementing agent provided by the embodiment comprises the following steps:
(1) 320g of ferric oxide, 2g of carbon nano tube and 40g of PEG-200 are weighed and placed in a ball mill for ball milling for 6 hours to obtain a first mixed material.
(2) 1454.6G of lithium acetate is weighed and added into the first mixed material, ball milling is continued for 6 hours, and a second mixed material with the D 50 particle size of 12.37 mu m is obtained.
(3) And (3) placing the second mixed material in a tube furnace, sintering and preserving heat for 15 hours at 800 ℃ in a nitrogen atmosphere according to a heating rate of 3 ℃/min, naturally cooling and crushing to obtain the lithium ferrite lithium supplement. The lithium ferrite lithium supplementing agent comprises lithium ferrite (chemical formula is Li 5FeO4) and a carbon coating layer coated on the surface of the lithium ferrite.
Example 2
The preparation method of the lithium ferrite lithium supplementing agent provided by the embodiment comprises the following steps:
(1) 320g of ferric oxide, 4g of graphite and 37g of PEG-200 are weighed and placed in a ball mill for ball milling for 8 hours to obtain a first mixed material.
(2) 1123.7G of lithium oxalate is weighed and added into the first mixed material, and ball milling is continued for 8 hours, so that a second mixed material with the D 50 particle size of 11.79 mu m is obtained.
(3) And (3) placing the second mixed material into a tube furnace, sintering and preserving heat for 20 hours at 700 ℃ in a nitrogen atmosphere according to a heating rate of 2 ℃/min, naturally cooling and crushing to obtain the lithium ferrite lithium supplement agent. The lithium ferrite lithium supplementing agent comprises lithium ferrite (chemical formula is Li 5FeO4) and a carbon coating layer coated on the surface of the lithium ferrite.
Example 3
The preparation method of the lithium ferrite lithium supplementing agent provided by the embodiment comprises the following steps:
(1) 320g of ferric oxide, 3.5g of graphene and 38g of PEG-200 are weighed and placed in a ball pick mill for ball milling for 7 hours, so as to obtain a first mixed material.
(2) 1454.6G of lithium acetate is weighed and added into the first mixed material, and ball milling is continued for 7 hours, so that a second mixed material with the D 50 particle size of 8.89 mu m is obtained.
(3) And (3) placing the second mixed material into a tube furnace, sintering and preserving heat for 18 hours at 750 ℃ in nitrogen atmosphere according to a heating rate of 4 ℃/min, naturally cooling and crushing to obtain the lithium ferrite lithium supplement agent. The lithium ferrite lithium supplementing agent comprises lithium ferrite (chemical formula is Li 5FeO4) and a carbon coating layer coated on the surface of the lithium ferrite.
Example 4
The preparation method of the lithium ferrite lithium supplementing agent provided by the embodiment comprises the following steps:
(1) 320g of ferric oxide, 6.5g of hydroxyethyl cellulose and 35g of PEG-200 are weighed and placed in a ball mill for ball milling for 6 hours to obtain a first mixed material.
(2) 1123.7G of lithium oxalate is weighed and added into the first mixed material, and ball milling is continued for 6 hours, so that a second mixed material with the D 50 particle size of 9.88 mu m is obtained.
(3) And (3) placing the second mixed material in a tube furnace, sintering and preserving heat for 15 hours at 750 ℃ in nitrogen atmosphere according to a heating rate of 3 ℃/min, naturally cooling and crushing to obtain the lithium ferrite lithium supplement agent. The lithium ferrite lithium supplementing agent comprises lithium ferrite (chemical formula is Li 5FeO4) and a carbon coating layer coated on the surface of the lithium ferrite.
Comparative example 1
The preparation method of the lithium ferrite lithium supplementing agent provided in this comparative example is the same as in example 1, except that 320g of iron oxide is replaced with 746g of ferrocene in step (1).
Comparative example 2
The preparation method of the lithium ferrite lithium supplement provided in this comparative example is the same as in example 1, except that 14544.6g of lithium acetate is replaced with 814.86g of lithium carbonate in step (2).
Comparative example 3
The preparation method of the lithium ferrite lithium supplementing agent provided in this comparative example is the same as that of example 1, except that carbon nanotubes and PEG-200 are not added in step (1).
Experimental example
XRD and SEM characterization were performed on the lithium ferrite lithium-supplementing agents prepared in each example and each comparative example, and indexes such as particle size, specific surface, element content, electric performance (first charge specific capacity at 0.05C) and the like of each lithium ferrite lithium-supplementing agent were detected, and the detection results are shown in Table 1.
The test standard of the electrical performance refers to detection of lithium iron phosphate anode materials (note that the air humidity requirement is less than or equal to 20%), the test method is electricity buckling (0.05C) detection, and lithium hexafluorophosphate is adopted as electrolyte.
Table 1 results of detection of respective indices of respective groups of lithium ferrite lithium-supplementing agents
The XRD pattern of the lithium ferrite lithium supplement prepared in example 1 is shown in FIG. 1, and the SEM patterns are shown in FIGS. 2 and 3. Wherein, the magnification of fig. 2 is 1000 times, and the magnification of fig. 3 is 10000 times.
From the above table 1, it can be seen that the electrochemical performance of the lithium ferrite lithium-supplementing agent prepared by the invention is more excellent, and the specific capacity of primary charge is higher.
While the invention has been illustrated and described with reference to specific embodiments, it is to be understood that the above embodiments are merely illustrative of the technical aspects of the invention and not restrictive thereof; those of ordinary skill in the art will appreciate that: modifications may be made to the technical solutions described in the foregoing embodiments, or equivalents may be substituted for some or all of the technical features thereof, without departing from the spirit and scope of the present invention; such modifications and substitutions do not depart from the spirit of the corresponding technical solutions; it is therefore intended to cover in the appended claims all such alternatives and modifications as fall within the scope of the invention.
Claims (11)
1. The preparation method of the lithium ferrite lithium supplementing agent is characterized by comprising the following steps of:
Mixing a carbon source, ferric oxide and an organic lubricant, and performing first grinding to obtain a first mixed material; the first mixed material is mixed with an organic lithium source and subjected to second grinding, so that a second mixed material is obtained; sintering the second mixed material to obtain the lithium ferrite lithium supplementing agent;
The ratio of the total mass of carbon elements in the carbon source and the organic lubricant to the mass of iron element in the iron oxide is 9.62-12.13%;
the organic lithium source comprises at least one of lithium acetate and lithium adipate;
The lithium ferrite lithium supplementing agent comprises lithium ferrite and a carbon coating layer coated on the surface of the lithium ferrite.
2. The method for preparing a lithium ferrite lithium supplement according to claim 1, wherein the carbon source comprises an inorganic carbon source and/or an organic carbon source.
3. The method for preparing a lithium ferrite lithium supplementing agent according to claim 2, wherein said inorganic carbon source comprises at least one of carbon nanotubes, graphene, graphite, C 60 and amorphous carbon;
And/or the organic carbon source comprises at least one of glucose, hydroxymethyl cellulose, soluble starch, hydroxyethyl cellulose, and petroleum pitch.
4. The method for preparing a lithium ferrite lithium supplement according to claim 1, wherein the organic lubricant comprises polyethylene glycol.
5. The method for preparing a lithium ferrite lithium supplementing agent according to claim 1, wherein a molar ratio of lithium element in the organic lithium source to iron element in the iron oxide is 5.05-5.8: 1.
6. The method for preparing a lithium ferrite lithium supplement according to claim 1, wherein the second mixed material has a D 50 particle size of 15 μm or less.
7. The method for preparing a lithium ferrite lithium supplementing agent according to claim 1, wherein the particle size of D 50 of the lithium ferrite lithium supplementing agent is less than or equal to 15 μm.
8. The method for preparing a lithium ferrite lithium supplementing agent according to claim 1, wherein the sintering temperature is 700-800 ℃, and the sintering heat preservation time is 15-20 h.
9. The method of claim 1, wherein the first grinding and/or the second grinding comprises ball milling.
10. The method for producing a lithium ferrite lithium supplement according to claim 1, wherein the time of the first grinding and/or the second grinding is 4 to 10 hours.
11. The use of the lithium ferrite lithium supplement prepared by the preparation method of the lithium ferrite lithium supplement according to any one of claims 1 to 10 in a lithium ion battery.
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| CN117776273B (en) * | 2024-02-23 | 2024-06-07 | 江苏维锂新能源材料有限公司 | Lithium supplementing agent, lithium iron phosphate battery repair material and preparation method thereof |
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