CN116282001B - Quality-improved graphite and preparation and application thereof - Google Patents
Quality-improved graphite and preparation and application thereof Download PDFInfo
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- CN116282001B CN116282001B CN202310284813.7A CN202310284813A CN116282001B CN 116282001 B CN116282001 B CN 116282001B CN 202310284813 A CN202310284813 A CN 202310284813A CN 116282001 B CN116282001 B CN 116282001B
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- fluoride
- chloride
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 134
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 123
- 239000010439 graphite Substances 0.000 title claims abstract description 123
- 238000002360 preparation method Methods 0.000 title description 2
- 238000011282 treatment Methods 0.000 claims abstract description 88
- 238000000034 method Methods 0.000 claims abstract description 65
- 239000000463 material Substances 0.000 claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000002994 raw material Substances 0.000 claims abstract description 19
- 239000002253 acid Substances 0.000 claims abstract description 16
- 238000005406 washing Methods 0.000 claims abstract description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 11
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 150000004673 fluoride salts Chemical class 0.000 claims description 24
- 229910021382 natural graphite Inorganic materials 0.000 claims description 23
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 22
- 150000003841 chloride salts Chemical class 0.000 claims description 18
- 230000008569 process Effects 0.000 claims description 18
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 16
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 12
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 11
- 235000013024 sodium fluoride Nutrition 0.000 claims description 11
- 239000011775 sodium fluoride Substances 0.000 claims description 11
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 10
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 8
- 235000019270 ammonium chloride Nutrition 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 230000001681 protective effect Effects 0.000 claims description 8
- 239000011780 sodium chloride Substances 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 238000000926 separation method Methods 0.000 claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 235000003270 potassium fluoride Nutrition 0.000 claims description 6
- 239000011698 potassium fluoride Substances 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 150000002221 fluorine Chemical class 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 239000011261 inert gas Substances 0.000 claims description 4
- -1 nitrate ions Chemical class 0.000 claims description 4
- 239000001103 potassium chloride Substances 0.000 claims description 4
- 235000011164 potassium chloride Nutrition 0.000 claims description 4
- 238000010306 acid treatment Methods 0.000 claims description 3
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- 239000012266 salt solution Substances 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- 150000001804 chlorine Chemical class 0.000 claims description 2
- 239000012141 concentrate Substances 0.000 claims description 2
- 239000004020 conductor Substances 0.000 claims description 2
- 238000005188 flotation Methods 0.000 claims description 2
- 238000002386 leaching Methods 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- 239000007770 graphite material Substances 0.000 abstract description 4
- 230000000694 effects Effects 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 8
- 230000006872 improvement Effects 0.000 description 8
- 239000007789 gas Substances 0.000 description 6
- 238000004321 preservation Methods 0.000 description 6
- 239000002131 composite material Substances 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 238000000746 purification Methods 0.000 description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 3
- 229910021383 artificial graphite Inorganic materials 0.000 description 3
- 125000001153 fluoro group Chemical group F* 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000004537 pulping Methods 0.000 description 2
- 238000011144 upstream manufacturing Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 239000013078 crystal 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
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000002391 graphite-based active material Substances 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 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
- C01B32/00—Carbon; Compounds thereof
- C01B32/20—Graphite
- C01B32/21—After-treatment
- C01B32/215—Purification; Recovery or purification of graphite formed in iron making, e.g. kish graphite
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/20—Graphite
- C01B32/21—After-treatment
-
- 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
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- 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)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention relates to the field of graphite materials, in particular to a graphite upgrading method, which comprises the following steps: carrying out first-stage heat-preserving and pressurizing treatment on a mixture containing graphite raw materials and fluoride under the conditions of pressure P1 and temperature T1, and then carrying out water treatment to obtain a treated material A; wherein the pressure P1 is greater than or equal to 1.5atm, and the temperature T1 is 200-350 ℃; step (2): carrying out second-stage heat-preserving and pressurizing treatment on the treatment material A and the chloride under the conditions of pressure P2 and temperature T2 to obtain a treatment material B; wherein the pressure P2 is greater than or equal to 5atm, and the temperature T2 is 300-600 ℃; step (3): and (3) washing the treated material B after acid liquor treatment to obtain the quality-improved graphite. The invention also comprises the material prepared by the method and application thereof. The method disclosed by the invention can improve the performance of graphite.
Description
Technical Field
The invention belongs to the field of graphite treatment, and particularly relates to the technical field of graphite quality improvement.
Background
The graphite has the advantages of higher specific capacity, low charge and discharge platform, stable circulation, low cost and the like, and is the most mainstream cathode material in the current lithium ion battery manufacturing. The graphite negative electrode material is divided into artificial graphite and natural graphite, and compared with artificial graphite, natural graphite has the advantages of low manufacturing cost, good low-temperature performance, good processability and the like, but is slightly lower than the artificial graphite negative electrode material in the aspects of rate performance, cycle performance, high-temperature performance and the like. Both have advantages and are suitable for different application occasions. The natural graphite has the advantages of no need of graphitization, safety and stability of an industrial chain supply chain and the like, the permeability in various application fields is gradually improved, and accordingly, the demand for upstream raw materials of the natural graphite cathode is continuously increased.
The upstream raw material of the natural graphite cathode is natural graphite ore which is naturally formed under special geological conditions such as high temperature, high pressure and the like, and the structure is lamellar graphite crystal. Naturally occurring graphite is rarely pure and typically contains impurities including metal oxides of silicon, aluminum, magnesium, calcium, and the like, and non-metal oxides of phosphorus, sulfur, vanadium, and the like. When the material is used as a battery cathode material, a purification step is needed first to ensure that the purity of the material meets the battery grade use requirement. At present, most of spheroidized materials for natural graphite cathode production are purified by mixed acid consisting of hydrochloric acid, nitric acid and hydrofluoric acid, and the deep impurity removal purpose can be realized by at least two acid treatments, so that the problems of long process flow, large waste acid amount, large treatment capacity of salt-containing wastewater and the like are caused. Therefore, the method simplifies the impurity removal process of the natural graphite and reduces the discharge of three wastes in the purification process, which is a technical problem to be solved urgently in the field.
Disclosure of Invention
In order to overcome the defects of the prior art, the first aim of the invention is to provide a graphite upgrading method, which aims to improve the upgrading effect and yield of graphite.
The second purpose of the invention is to provide the upgraded graphite obtained by the upgrading method, and aims to obtain an upgraded graphite material with characteristic properties and morphology and excellent performance.
A third object of the invention is to provide the use of said upgraded graphite.
A fourth object of the present invention is to provide an electrode comprising said upgraded graphite and a device such as a battery comprising said electrode.
Graphite raw materials such as natural graphite generally contain more ash and impurities, and the purity and application performance of the graphite raw materials can be improved by purifying the graphite raw materials, however, the existing purification means have better effect on improving the purity, but the yield is not ideal, and the microstructure and the active surface of the graphite raw materials are difficult to synchronously upgrade and repair, and the performance such as electrochemical performance needs to be improved. In view of this problem, the present invention provides the following solutions:
a method for upgrading graphite, comprising the steps of:
step (1): carrying out first-stage heat-preserving and pressurizing treatment on a mixture containing graphite raw materials and fluoride under the conditions of pressure P1 and temperature T1, and then carrying out water treatment to obtain a treated material A;
wherein the pressure P1 is greater than or equal to 1.5atm, and the temperature T1 is 200-350 ℃;
step (2): carrying out second-stage heat-preserving and pressurizing treatment on the treatment material A and the chloride under the conditions of pressure P2 and temperature T2 to obtain a treatment material B;
wherein the pressure P2 is greater than or equal to 5atm, and the temperature T2 is 300-600 ℃;
step (3): and (3) washing the treated material B after acid liquor treatment to obtain the quality-improved graphite.
Aiming at the problem that graphite is difficult to upgrade, the invention innovatively combines the first stage of pressurizing and heat-preserving multiphase treatment assisted by fluoride salt and the second stage of pressurizing and heat-preserving multiphase treatment assisted by chloride salt, and further cooperates with the combined control of T1-P1/T2/P2 parameters of the treatment sequence and the treatment stage, so that the synergy can be realized, the separation of graphite carbon and other components can be realized accidentally and selectively, the yield and purity can be improved, and the microstructure and the surface groups can be repaired and reconfigured, so that the performance, particularly the electrochemical performance, of the material can be synchronously improved.
According to the technical scheme, the initial quality of the graphite raw material is not particularly required, and for example, the graphite raw material can be natural graphite with any quality. For another example, the natural graphite is graphite concentrate obtained by a flotation method. Further, the carbon content of the natural graphite is 60wt.% or more, preferably 70 to 95wt.%, and may be further 75 to 85wt.% in consideration of the process value.
In the invention, the graphite raw material is spheroidized graphite, and the particle size of the spheroidized graphite is 5-20 mu m.
In the invention, the heat-preservation and pressurizing treatment thought assisted by fluoride salt and chloride salt and the combined control of treatment process parameters are key to cooperatively realize the quality improvement of graphite. The research also finds that the components of fluoride salt and chloride salt in the treatment stage and the pressurizing and heat-preserving treatment mode and conditions in the treatment stage are further controlled, thereby being beneficial to further improving the quality improvement treatment effect of the graphite.
Preferably, the fluoride salt is at least one of ammonium fluoride, lithium fluoride, sodium fluoride and potassium fluoride; further preferably, the fluorine salt is two or more of ammonium fluoride, lithium fluoride, sodium fluoride and potassium fluoride. It was found that the use of the combined fluoride salt helps to further synergistically improve the quality improving effect and yield of graphite.
Preferably, the fluoride salt is ammonium fluoride and sodium fluoride, and the molar ratio of the ammonium fluoride to the sodium fluoride is 1-2:1-2. It has been found that the combination of the preferred fluoride salts in combination with the combined control of treatment pressure and temperature according to the invention can further improve the synergy and can further improve the effect.
Preferably, the graphite raw material and the fluoride salt solution are impregnated in advance, and then dried to obtain the mixture;
Preferably, the weight ratio of the graphite raw material to the fluorine salt is 1:0.01 to 0.2, and further may be 1:0.02 to 0.06 in view of the processing cost.
In the invention, in the first section of heat preservation and pressurization treatment process of the step (1), the atmosphere A is adopted for pressurization; the atmosphere A comprises a protective atmosphere;
Preferably, the protective atmosphere is at least one of nitrogen and inert gas.
Preferably, the atmosphere a further contains not more than 10% by volume, preferably 1 to 5% by volume, of water vapor. According to the invention, under the thought of fluoride salt-assisted pressurizing and heat-preserving treatment, the combination control of the pressurizing atmosphere containing a small amount of water vapor is further matched, so that the quality improvement effect and the yield can be further synergistically improved.
Preferably, the pressure of the P1 is 2-3 atm;
Preferably, the temperature of T1 is 250-300 ℃;
Preferably, the pressure and heat preservation treatment time under the conditions of P1 and T1 is 0.5-3 h, and further can be 1-2 h in consideration of treatment effect and cost;
Preferably, in step (1), the water treatment comprises an aqueous solution washing process, the aqueous solution is for example water, a mixed solution of water and an organic solvent, and the organic solvent is for example a solvent which can be miscible with water and can be at least one of C1-C4 alcohol, propanol and THF;
Preferably, the washing mode is solid-liquid separation after leaching or soaking;
the temperature of the water treatment stage is not particularly limited, and may be, for example, 10 to 80℃and room temperature is preferred in view of process simplicity and treatment cost.
According to the invention, after the first stage of pressurization and heat preservation treatment assisted by fluoride salt is performed, the subsequent gradient pressurization and heat-up treatment assisted by chloride salt is further matched, so that the quality improvement effect and yield of graphite are further synergistically improved.
Preferably, the chloride salt is at least one of ammonium chloride, lithium chloride, sodium chloride and potassium chloride, and preferably two or more. It was found that under the preferred chloride salts, the upgrading effect can be further synergistically improved.
Preferably, the chloride salt is sodium chloride or ammonium chloride. The invention researches find that under the condition of the preferable combined chloride salt, the combined temperature and pressure increasing process can be combined with the temperature and pressure increasing process, so that the synergistic effect can be further improved, and the performance of the treated material can be further improved.
Preferably, the weight ratio of the graphite raw material to the chloride salt is 1:0.01 to 0.2, more preferably 1:0.02 to 0.06.
In the invention, in the second section of heat preservation and pressurization treatment process of the step (2), the atmosphere B is adopted for pressurization; the atmosphere B comprises a protective atmosphere;
Preferably, the protective atmosphere is at least one of nitrogen and inert gas;
Preferably, the atmosphere B further contains ammonia in an amount of not more than 10% by volume, preferably 1 to 5% by volume. The research shows that the pressurization treatment is carried out by adopting a trace ammonia-containing atmosphere, which is favorable for further cooperating with other operations and can further synergistically improve the quality improvement effect of the graphite.
According to the invention, under the thought of two-stage pressurizing heat-preserving treatment of fluoride salt and chloride salt, the parameter control of gradient heating and boosting is further matched, so that the quality improvement effect of graphite is further synergistically improved.
Preferably, the pressure of the P2 is 5-10 atm;
Preferably, the temperature of T2 is 400-600 ℃;
preferably, the pressure maintaining and heat preserving treatment time under the conditions of P2 and T2 is 1-5 h;
preferably, after the second-stage heat-preserving pressurizing treatment, water treatment is performed in advance, and then the treatment of the step (3) is performed; the water treatment is water leaching-solid-liquid separation or water washing treatment.
In the step (3), the acid liquid is a mixed aqueous solution of hydrochloric acid, nitric acid and hydrofluoric acid;
preferably, in the acid liquor, the H+ concentration is 0.15-0.5mol/L, the chloride ion concentration is 0.05-0.2mol/L, the nitrate ion concentration is 0.05-0.2mol/L, and the fluoride ion concentration is 0.05-0.2mol/L;
Preferably, the liquid-to-solid weight ratio (1-10) ml/g of the acid treatment stage;
preferably, the upgraded graphite is obtained by washing the treated graphite with water to be neutral and drying the treated graphite.
The invention relates to a preferred graphite upgrading method, which comprises the following steps:
the first step:
adding the spheroidized natural graphite to be purified into a fluoride salt solution, slowly drying at a low temperature, then heating to 200-350 ℃, preserving heat for 0.5-3 hours, and pressurizing by adopting atmosphere A in the heating and preserving heat stages, wherein the pressure is maintained to be 2-3 atm; then mixing the mixture with water for pulping, then carrying out solid-liquid separation, washing and drying to obtain a treated material A;
the fluoride salt is preferably one or more of ammonium fluoride, lithium fluoride, sodium fluoride and potassium fluoride, and the mass ratio of the fluoride salt to the graphite is 1-20%;
And a second step of:
adding chloride with the mass ratio of 1-20% into the treatment material A, uniformly mixing, and then adopting atmosphere B to carry out pressurized heat treatment, wherein the temperature of the heat treatment is 300-600 ℃, the pressure is 5-10 atm, and the time is 1-5 hours;
and a third step of:
adding the treatment material B into mixed acid consisting of dilute hydrochloric acid, dilute nitric acid and dilute hydrofluoric acid for treatment, wherein the H+ concentration in the mixed acid is 0.15-0.5mol/L, chloride ion is 0.05-0.2mol/L, nitrate ion is 0.05-0.2mol/L, fluoride ion is 0.05-0.2mol/L, and the liquid-solid ratio (1-10): and 1, filtering after the reaction is finished, washing filter residues with deionized water until the pH value of the supernatant is 7, and drying to obtain the upgraded graphite.
The invention also provides the upgraded graphite prepared by the graphite upgrading method.
In the invention, the control of the upgrading process can endow the material with special microstructure and properties, and the upgrading method can obtain excellent performance.
The invention also provides an application of the upgraded graphite prepared by the graphite upgrading method, and the upgraded graphite is used for preparing at least one of a graphite electrode and a heat conducting material;
preferably, the graphite cathode is prepared by using the method.
In the present invention, any graphite-containing materials and devices may be prepared according to known means.
For example, the invention also provides a graphite electrode and a battery, wherein the negative electrode comprises the upgraded graphite prepared by the graphite upgrading method.
Advantageous effects
The invention can realize the purification and quality improvement of graphite and improve the yield, purity and performance of graphite based on the treatment process.
The process can reduce the treatment temperature, reduce the acid liquor and wastewater output, has simple process and lower energy consumption, and is easy to realize mass production.
Drawings
FIG. 1 is an SEM image of a graphite material after the third-stage treatment of example 1;
FIG. 2 is an XRD pattern of the graphite material after the third step of treatment of example 1;
Detailed Description
The invention is further illustrated below in connection with specific examples, which are not to be construed as limiting in any way.
In each example and comparative example of the present invention, the spheroidized natural graphite to be purified is a natural graphite powder (hereinafter, the natural graphite used in the case is the natural graphite powder unless specifically stated otherwise) obtained by concentrating and spheroidizing graphite ore, the average particle size thereof is 15 μm, the carbon content thereof is 87.2%, and the main impurities and the carbon content thereof are shown in the following table.
| SiO2 | Fe2O3 | Al2O3 | MgO | CaO | K2O | TiO2 | ZrO | MnO | P2O5 | S | C |
| 4.78 | 4.63 | 1.85 | 0.36 | 0.32 | 0.11 | 0.14 | 0.54 | 0.01 | 0.01 | 0.05 | 87.2 |
The graphite purity detection method is carried out according to GB/T3518-2008.
In the present invention, the atm refers to the atmospheric pressure.
Electrochemical performance test: the CR2025 button cell is assembled in a dry glove box filled with argon by taking the graphite electrode (the final prepared quality-improving graphite active material of each case, acetylene black and PVDF are 90:5:5 in weight ratio) as a working electrode, lithium metal as a negative electrode, EC/EMC (volume ratio 1:1) of 1mol/L LiPF6 as electrolyte and PE-PP composite film as a diaphragm, and the battery charge and discharge detection is carried out at the temperature of 40 ℃ and the voltage interval of 0.001-2V and the current density of 74 mA/g.
Example 1
The first step:
Adding natural graphite into a fluoride salt (ammonium fluoride in the case) solution with the concentration of 0.5mol/L, wherein the mass ratio of the fluoride salt to the graphite is 5%; after slow drying at low temperature (temperature is 60 ℃), heating to 200 ℃ (marked as T1), preserving heat for 1 hour, and pressurizing and maintaining pressure through atmosphere A (nitrogen in this case) in the heating and preserving heat stage, wherein the pressure P1 is 2atm; cooling and decompressing after heat preservation treatment, pulping in water, filtering, washing with water, and drying to obtain a treated material A;
And a second step of:
Uniformly mixing a treatment material A and chloride (ammonium chloride in this case, 5% of the dry weight of the treatment material A), and then introducing an atmosphere B (nitrogen in this case) to perform pressurizing and heating treatment, wherein the pressure P2 is 5atm, the temperature T2 is 400 ℃, and the heat and pressure maintaining treatment time is 2 hours to obtain a treatment material B;
and a third step of:
Adding the treatment material B into a mixed acid solution composed of dilute hydrochloric acid, dilute nitric acid and dilute hydrofluoric acid for treatment, wherein in the mixed acid solution, chloride ions are 0.05mol/L, nitrate ions are 0.05mol/L, fluoride ions are 0.05mol/L, and the liquid-solid ratio in the treatment stage is 5ml/g; and then solid-liquid separation, washing with water to neutrality and drying to obtain the quality-improved graphite.
Example 2
The only difference compared to example 1 is that the fluoride salt type of step 1 was changed, the experimental group was:
Group A: the combined fluoride salt in the step 1 is ammonium fluoride and sodium fluoride in a weight ratio of 1:1, and the total amount is 3wt% of graphite;
group B: the combined fluoride salt in the step 1 is potassium fluoride and sodium fluoride in a weight ratio of 1:1, and the total amount is 3wt% of graphite;
Other operations and parameters were the same as in example 1.
Example 3
The only difference compared to example 1 is that atmosphere a and P1 and T1 of step 1 are changed, the experimental group is:
group A: atmosphere A is a water vapor-nitrogen composite gas containing 5% by volume;
group B: t1 has a temperature of 300 ℃, and P1 has a pressure of 3atm;
group C: t1 has a temperature of 250 ℃, and P1 has a pressure of 2.5atm;
Other operations and parameters were the same as in example 1.
Example 4
The difference compared with example 1 is only that the chloride type of step 2 is changed, and the experimental group is:
a: the combined chloride salt in the step 2 is prepared from the following components in percentage by mass: 1, wherein the total amount of the ammonium chloride and the sodium chloride is 3wt% of the graphite;
b: the combined chloride salt in the step 2 is prepared from the following components in percentage by mass: 1, wherein the total amount of potassium chloride and sodium chloride is 3wt% of graphite;
Other operations and parameters were the same as in example 1.
Example 5
The only difference compared to example 1 is that atmosphere B and P2 and T2 of step 2 are changed, the experimental set is:
group A: atmosphere A is an ammonia-nitrogen composite gas containing 5% by volume.
Group B: t2 has a temperature of 600 ℃, and P2 has a pressure of 5atm;
Group C: t2 has a temperature of 500 ℃, and P2 has a pressure of 6atm;
Other operations and parameters were the same as in example 1.
Example 6
The difference from example 1 is only that the conditions of steps 1 to 3 are changed, and that:
group A: in the step1, the fluorine salt is ammonium fluoride and sodium fluoride in a weight ratio of 1:1, the atmosphere A is 5v% of water vapor-nitrogen composite gas, the temperature of T1 is 250 ℃ in a weight ratio, and the pressure of P1 is 2.5atm;
Group B: in the step 2, the chlorine salt is ammonium chloride and sodium chloride in a weight ratio of 1:1, the atmosphere B is 5% ammonia-nitrogen composite gas, the temperature of T2 is 500 ℃, and the pressure of P1 is 6atm;
other operations and parameters were the same as in example 1.
Example 7
The only difference compared with example 1 is that the mixed acid solution and conditions of step 3 are changed, specifically:
In the mixed acid solution, the liquid-solid ratio of chloride ion 0.1mol/L, nitrate ion 0.1mol/L and fluoride ion 0.1mol/L in the treatment stage is 3ml/g, and other operations and parameters are the same as in example 1.
Comparative example 1 (comparative case where a single chloride salt was subjected to two-stage treatment)
The only difference compared to example 1 is that the fluoride salt of step 1 is replaced with an equal weight of chloride salt (same as step 2), other operations and parameters are the same as in example 1.
Comparative example 2 (comparative case where a single fluoro salt was subjected to two-stage treatment)
The only difference compared to example 1 is that the chloride salt of step 2 is replaced with an equal weight of fluoride salt (same as in step 1), other operations and parameters are the same as in example 1.
Comparative example 3 (comparative case with chlorine before fluorine)
The difference compared to example 1 is only that the fluoro salt of step1 is replaced with an equal weight of chloro salt (same as step2 of example 1) and the chloro salt of step2 is replaced with an equal weight of fluoro salt (same as step1 of example 1), other operations and parameters are the same as example 1.
Comparative example 4 (non-gas pressurized treatment)
The difference compared to example 1 is only that no gas pressurization treatment was performed for steps 1 and/or 2, the experimental groups being:
A: in step 1, the pressurizing treatment was not performed, that is, the pressure in the treatment stage was normal pressure, and the other operations were the same as in example 1.
B: in step2, the pressurizing treatment was not performed, that is, the pressure in the treatment stage was normal pressure, and the other operations were the same as in example 1.
C: in both steps 1 and 2, no pressure treatment was performed, and other operations and parameters were the same as in example 1.
Comparative example 5 (changing the temperature and pressure of the second stage treatment)
The difference compared with example 1 is that in step2, the control conditions of P2 and T2 are the same as those of P1 and T1 in step 1, and other operations and parameters are the same as those of example 1.
Comparative example 6
The difference compared with example 1 is that steps 1 and 2 are omitted, and the natural graphite is directly subjected to the treatment of step 3, and other operations and parameters are the same as in example 1.
The test results of the materials obtained in the above examples and comparative examples are as follows:
From the above data, it is clear that with the method of the present invention, a good carbon recovery effect can be obtained, and not only that, but also that the electrochemical properties of the resulting material at relatively high temperatures can be improved.
Claims (36)
1. A method for upgrading graphite, comprising the steps of:
Step (1): carrying out first-stage heat-preserving and pressurizing treatment on a mixture containing graphite raw materials and fluoride under the conditions of pressure P1 and temperature T1, and then carrying out water treatment to obtain a treated material A; the fluoride salt is at least one of ammonium fluoride, lithium fluoride, sodium fluoride and potassium fluoride;
wherein the pressure P1 is greater than or equal to 1.5atm, and the temperature T1 is 200-350 ℃;
Step (2): carrying out second-stage heat-preserving and pressurizing treatment on the treatment material A and the chloride under the conditions of pressure P2 and temperature T2 to obtain a treatment material B; the chloride salt is at least one of ammonium chloride, lithium chloride, sodium chloride and potassium chloride;
wherein the pressure P2 is greater than or equal to 5atm, and the temperature T2 is 300-600 ℃;
step (3): and (3) washing the treated material B after acid liquor treatment to obtain the quality-improved graphite.
2. The method for upgrading graphite according to claim 1, wherein the graphite raw material is natural graphite.
3. The method for upgrading graphite according to claim 2, wherein the natural graphite is a graphite concentrate obtained by a flotation method.
4. The method of upgrading graphite according to claim 2, wherein the natural graphite has a carbon content of greater than or equal to 60wt.%.
5. The method for upgrading graphite according to claim 4, wherein the natural graphite has a carbon content of 70-95 wt.%.
6. The method for upgrading graphite according to claim 1, wherein the fluoride salt is two or more of ammonium fluoride, lithium fluoride, sodium fluoride and potassium fluoride.
7. The method for upgrading graphite of claim 6, wherein the fluoride salt is ammonium fluoride or sodium fluoride.
8. The method for upgrading graphite according to claim 1, wherein the graphite raw material and the fluorine salt solution are impregnated in advance, followed by drying to obtain the mixture.
9. The method for upgrading graphite according to claim 1, wherein the weight ratio of the graphite raw material to the fluorine salt is 1:0.01 to 0.2.
10. The graphite upgrading method according to claim 1, wherein in the first-stage heat-preserving pressurizing treatment of the step (1), pressurizing is performed by adopting an atmosphere a; the atmosphere A comprises a protective atmosphere.
11. The method for upgrading graphite according to claim 10, wherein the protective atmosphere is at least one of nitrogen and an inert gas.
12. The method of upgrading graphite according to claim 10, wherein the atmosphere a further comprises not more than 10v% of water vapor.
13. The graphite upgrading process according to claim 1, wherein the pressure of P1 is 2 to 3atm.
14. The method for upgrading graphite according to claim 1, wherein the temperature of T1 is 250-300 ℃.
15. The graphite upgrading method according to claim 1, wherein the pressure maintaining and heat preserving treatment time under the conditions of P1 and T1 is 0.5-3 h.
16. The method of upgrading graphite according to claim 1, wherein in step (1), the water treatment comprises an aqueous solution washing process.
17. The method for upgrading graphite according to claim 16, wherein the washing mode is solid-liquid separation after leaching or soaking.
18. The graphite upgrading process according to claim 1, wherein the water treatment stage is at a temperature of 50-80 ℃.
19. The method for upgrading graphite according to claim 1, wherein the chloride salt is two or more of ammonium chloride, lithium chloride, sodium chloride and potassium chloride.
20. The method for upgrading graphite according to claim 19, wherein the chloride salt is sodium chloride or ammonium chloride.
21. The method for upgrading graphite according to claim 1, wherein the weight ratio of graphite raw material to chlorine salt is 1:0.01 to 0.2.
22. The graphite upgrading method according to claim 1, wherein in the second-stage heat-preserving pressurizing treatment of the step (2), pressurizing is performed by adopting an atmosphere B; the atmosphere B comprises a protective atmosphere.
23. The method for upgrading graphite according to claim 22, wherein in atmosphere B, the protective atmosphere is at least one of nitrogen and inert gas.
24. The method of upgrading graphite according to claim 22, wherein the atmosphere B further comprises not more than 10v% ammonia.
25. The method for upgrading graphite according to claim 1, wherein the pressure of P2 is 5to 10atm.
26. The method for upgrading graphite according to claim 1, wherein the temperature of T2 is 400-600 ℃.
27. The graphite upgrading method according to claim 1, wherein the pressure maintaining and heat preserving treatment time under the conditions of P2 and T2 is 1-5 h.
28. The graphite upgrading method according to claim 1, wherein after the second-stage heat-preserving pressurizing treatment, water treatment is performed in advance, followed by the treatment of step (3); the water treatment is water leaching-solid-liquid separation or water washing treatment.
29. The method for upgrading graphite according to claim 1, wherein in the step (3), the acid solution is a mixed aqueous solution of hydrochloric acid, nitric acid and hydrofluoric acid.
30. The method for upgrading graphite according to claim 29, wherein the acid solution has a h+ concentration of 0.15-0.5mol/L, chloride ions of 0.05-0.2mol/L, nitrate ions of 0.05-0.2mol/L and fluoride ions of 0.05-0.2mol/L.
31. The graphite upgrading process according to claim 1, wherein the acid treatment stage has a liquid to solid volume weight ratio of 1-10 ml/g.
32. The method for upgrading graphite according to claim 1, wherein the upgraded graphite is obtained by washing the treated graphite with water to neutrality and drying the treated graphite.
33. A upgraded graphite produced by the graphite upgrading process of any one of claims 1 to 32.
34. Use of the upgraded graphite produced by the graphite upgrading method according to any one of claims 1-32, for the production of at least one of graphite electrodes and heat conducting materials.
35. Use of the upgraded graphite produced by the graphite upgrading process of claim 34 for the production of graphite negative electrodes.
36. A graphite battery, characterized in that the negative electrode of the graphite battery comprises the upgraded graphite prepared by the graphite upgrading method of any one of claims 1-32.
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| CN115498185A (en) * | 2022-09-21 | 2022-12-20 | 湖南宸宇富基新能源科技有限公司 | Regeneration method of waste graphite negative electrode material |
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