CN116621154A - Preparation method of battery cathode material, electrode thereof and battery - Google Patents
Preparation method of battery cathode material, electrode thereof and battery Download PDFInfo
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- CN116621154A CN116621154A CN202310630492.1A CN202310630492A CN116621154A CN 116621154 A CN116621154 A CN 116621154A CN 202310630492 A CN202310630492 A CN 202310630492A CN 116621154 A CN116621154 A CN 116621154A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000010406 cathode material Substances 0.000 title claims abstract description 11
- 239000003245 coal Substances 0.000 claims abstract description 131
- 238000005188 flotation Methods 0.000 claims abstract description 93
- 239000000463 material Substances 0.000 claims abstract description 84
- 239000002245 particle Substances 0.000 claims abstract description 59
- 238000000576 coating method Methods 0.000 claims abstract description 50
- 239000011248 coating agent Substances 0.000 claims abstract description 49
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 37
- 238000011282 treatment Methods 0.000 claims abstract description 34
- 239000010405 anode material Substances 0.000 claims abstract description 30
- 238000010306 acid treatment Methods 0.000 claims abstract description 25
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000003513 alkali Substances 0.000 claims abstract description 24
- 239000000843 powder Substances 0.000 claims abstract description 22
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 20
- 238000007885 magnetic separation Methods 0.000 claims abstract description 20
- 238000007873 sieving Methods 0.000 claims abstract description 14
- 238000010000 carbonizing Methods 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 36
- 239000005539 carbonized material Substances 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 23
- 239000007864 aqueous solution Substances 0.000 claims description 20
- 229910052742 iron Inorganic materials 0.000 claims description 18
- 239000002817 coal dust Substances 0.000 claims description 16
- 239000010426 asphalt Substances 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 13
- 230000001681 protective effect Effects 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 11
- 239000013077 target material Substances 0.000 claims description 10
- RHZUVFJBSILHOK-UHFFFAOYSA-N anthracen-1-ylmethanolate Chemical compound C1=CC=C2C=C3C(C[O-])=CC=CC3=CC2=C1 RHZUVFJBSILHOK-UHFFFAOYSA-N 0.000 claims description 9
- 239000003830 anthracite Substances 0.000 claims description 9
- 238000002791 soaking Methods 0.000 claims description 9
- 238000003763 carbonization Methods 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 239000003077 lignite Substances 0.000 claims description 5
- 239000010439 graphite Substances 0.000 claims description 4
- 229910002804 graphite Inorganic materials 0.000 claims description 4
- 239000002585 base Substances 0.000 claims description 3
- 238000004939 coking Methods 0.000 claims description 3
- 229920000098 polyolefin Polymers 0.000 claims description 3
- 230000002378 acidificating effect Effects 0.000 claims description 2
- 150000001720 carbohydrates Chemical class 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 238000010902 jet-milling Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 4
- 239000011347 resin Substances 0.000 claims 1
- 229920005989 resin Polymers 0.000 claims 1
- 239000012535 impurity Substances 0.000 abstract description 12
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 11
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 11
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 abstract description 3
- 230000002441 reversible effect Effects 0.000 abstract description 3
- 229910001415 sodium ion Inorganic materials 0.000 abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 10
- 239000007773 negative electrode material Substances 0.000 description 10
- 230000018044 dehydration Effects 0.000 description 7
- 238000006297 dehydration reaction Methods 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 238000012545 processing Methods 0.000 description 6
- 230000002829 reductive effect Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 238000000605 extraction Methods 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- -1 transition metal nitride Chemical class 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000005587 carbonate group Chemical group 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229910052723 transition metal 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
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- 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)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to a preparation method of a battery cathode material, an electrode and a battery thereof, and the preparation method of the battery cathode comprises the following steps: obtaining coal particles with the granularity of less than 10 mm; mixing the coal particles, water and heavy media, and performing flotation to obtain primary flotation coal particles; crushing to obtain coal powder; performing secondary flotation, and then performing magnetic separation to obtain pulverized coal; then alkali treatment and acid treatment are carried out to obtain coarse materials; and finally, carbonizing, coating and scattering carbon, and sieving to obtain the battery anode material. The invention can reduce ash content of coal with higher impurity content by advanced beneficiation treatment, meets the requirement of preparing the battery cathode material, expands raw material sources, improves the added value of raw materials, and has high reversible gram capacity of both lithium ion batteries and sodium ion batteries, and excellent market application prospect.
Description
Technical Field
The invention relates to a battery material, in particular to a preparation method of a battery negative electrode material, an electrode thereof and a battery.
Background
The battery negative electrode materials generally comprise carbon negative electrode materials, silicon-based negative electrode materials, lithium-containing transition metal nitride negative electrode materials, alloy negative electrode materials, nanoscale negative electrode materials and the like, and the carbon negative electrode materials are taken as examples, have wide sources and are the most common battery negative electrodes. The preparation method of the carbon anode material mainly focuses on the formation process of the material at present, and the treatment attention to impurities is not high.
Taking coal as an example, the coal has wide sources and low price, and is concerned by a plurality of scholars and enterprises. How to improve the performance of a battery anode obtained by coal processing is the key point of current research, for example, patent application CN105720233a discloses a preparation method of a carbon material for a lithium ion battery anode, which comprises the following steps: polymerizing the coal liquefaction residues; and (3) stabilizing the polymerization product, and carbonizing the stabilized product to obtain the carbon material for the lithium ion battery cathode. The method utilizes the coal liquefaction residues for processing, and has limited sources; under the conditions that the extraction pressure is 0-3MPa, the extraction temperature is not higher than 300 ℃, the extraction time is more than 5 minutes and the stirring rate is 50-400r/min, the direct coal liquefaction residues with the mass ratio of 1:1-10 and the first extraction solvent are added into an extraction device, and heavy liquefied oil components in the direct coal liquefaction residues are extracted, so that the cost is high, and the industrial popularization and application are not facilitated.
Disclosure of Invention
The invention aims to overcome the difficulty of limited performance of a battery cathode obtained by existing coal processing, and provides a preparation method of a battery cathode material.
The invention uses coal as initial raw material, while the natural coal inevitably contains some impurity, and the battery material has high impurity demand, therefore, the invention combines 2 times of floatation and 1 times of magnetic separation and multiple times of crushing, gradually reduces ash content in the coal, and after reaching the ash content not more than 0.8%, the operations of carbonization, cladding and the like are carried out, thus ensuring the cathode material to have high electrochemical activity.
In the preparation method, the ash impurity content of silicon, silicon dioxide and the like is reduced by physical impurity removal and chemical impurity removal so as to ensure the electrochemical activity of the product, wherein it is critical how to combine the ore dressing and impurity removal process, namely the sequence of the steps, so as to improve the quality of the product and reduce the cost.
Since lithium ion batteries produce irreversible compounds due to charge and discharge, it is necessary to reduce the contents of silicon and silicon dioxide and metals such as iron or metal ions in the negative electrode material as much as possible. The invention removes massive impurities through physical mineral separation, and removes some tiny impurities such as slag inclusion and the like through combining chemical mineral separation after full crushing, thereby ensuring that the ash content in the material is as low as possible.
The specific scheme is as follows:
the preparation method of the battery anode material comprises the following steps:
(1) Obtaining coal particles with the granularity of less than 10 mm;
(2) Subjecting the coal particles to primary flotation: mixing the coal particles, water and heavy media, adopting a heavy media flotation machine to process, collecting target materials, carrying out primary magnetic separation, and dehydrating to obtain primary flotation coal particles;
(3) Crushing the primary flotation coal particles to obtain coal dust;
(4) Performing secondary flotation on the pulverized coal, and performing secondary magnetic separation on a flotation liquid obtained by flotation to obtain the pulverized coal;
(5) Performing alkali treatment and acid treatment on the pulverized coal to obtain coarse materials;
(6) Carbonizing the coarse material in a protective atmosphere to obtain carbonized material;
(7) Carbon coating is carried out on the carbonized material in a protective atmosphere to obtain a coated material;
(8) And scattering and sieving the coating material to obtain the battery anode material.
Further, in the step (1), coal is used as a raw material, and at least one of coking coal, gas coal, lignite, anthracite, long flame coal and lean coal is included, wherein the mass content of ash in the coal is 5-20%.
Further, in the step (2), the mass ratio of the coal particles, the water and the heavy medium are mixed is as follows: 10-30:30-50:10-25, preferably 10-20:30-40:10-20 parts of a base; preferably, the heavy medium is iron ore powder; the mass content of ash in the primary flotation coal particles obtained through primary flotation is 1.5-5%.
Further, in step (3), the powder is crushed until D90 is less than 10um.
Further, the ash content of the pulverized coal in the step (4) is 0.8-1.5% by mass;
optionally, the secondary flotation uses water as a medium.
Further, in the step (5), an alkaline aqueous solution with the concentration of 5-80wt% is adopted for the alkali treatment, the pulverized coal and the alkaline aqueous solution are mixed and then are subjected to heating treatment, and then the mixture is filtered and washed until the pH value is less than 8.5; the acid treatment adopts an acidic aqueous solution with the concentration of 0.1-30wt%, and the pH value is more than 5.5 after soaking, filtering and washing;
preferably, the alkali treatment and the acid treatment are repeated for 1-2 times, and the mass content of ash content of the coarse material obtained by the alkali treatment and the acid treatment is 0.2-0.8%
Further, the temperature of carbonization treatment in the step (6) is 1000-2000 ℃ and the time is 1-5h;
optionally, in the step (7), the carbon is coated by at least one of saccharides, asphalt, graphite, polyolefin, phenol and phenol derivatives, wherein the temperature is 500-1000 ℃ and the time is 1-5h;
optionally, in the step (8), the scattering adopts a jet milling mode, and then the powder is sieved by a 100-300 mesh sieve to obtain the battery cathode material.
The invention also provides the battery anode material prepared by the preparation method of the battery anode material.
The invention also provides an electrode, which comprises the battery anode material.
The invention also provides a battery comprising the electrode.
The beneficial effects are that:
in the invention, the preparation method of the battery anode material uses various types of coal materials, so that impurities in coal can be reduced to a reasonable range, for example, anthracite with high ash content can be reduced to within 1%, and more preferably, the content can be less than 0.5%.
Furthermore, the coal material subjected to multiple treatments in the invention combines carbonization and coating technologies, and the formed anode material has good charge-discharge activity. In a half-battery system, the capacity of the lithium ion battery is 300mAh/g in the first reversible gram and 220mAh/g in the first reversible gram at 0.01-3V and 0.1C, and the lithium ion battery has a good industrial application prospect.
Drawings
In order to more clearly illustrate the technical solutions of the present invention, the following brief description will be made on the accompanying drawings, which are given by way of illustration only and not limitation of the present invention.
FIG. 1 is a graph of cycle performance provided by one embodiment 1 of the present invention;
FIG. 2 is a charge-discharge graph provided in comparative example 1 of the present invention;
FIG. 3 is a graph of the cycle performance provided by comparative example 1 of the present invention;
fig. 4 is a charge-discharge graph provided in comparative example 2 of the present invention.
Detailed Description
Definitions of some of the terms used in the present invention are given below, and other unrecited terms have definitions and meanings well known in the art:
the preparation method of the battery cathode material comprises the following steps:
(1) Obtaining coal particles with the granularity of less than 10 mm;
(2) Subjecting the coal particles to primary flotation: mixing the coal particles, water and heavy media, adopting a heavy media flotation machine to process, collecting target materials, and dehydrating to obtain primary flotation coal particles;
(3) Crushing the primary flotation coal particles to obtain coal dust;
(4) Performing secondary flotation on the pulverized coal, wherein the secondary flotation is the same as the primary flotation, and performing magnetic separation on a flotation liquid obtained by flotation to obtain the pulverized coal;
(5) Performing alkali treatment and acid treatment on the pulverized coal to obtain coarse materials;
(6) Carbonizing the coarse material in a protective atmosphere to obtain carbonized material;
(7) Carbon coating is carried out on the carbonized material to obtain a coated material;
(8) And scattering and sieving the coating material to obtain the battery anode material.
The coal is not limited in kind, and can be at least one of coking coal, gas coal, lignite, anthracite, long flame coal and lean coal, and the mass content of ash in the coal is 5-20%. Anthracite is preferably used as a material, and the ash content of the anthracite is generally 5-12%; the conventional anthracite is in a block shape, and coarse powder is carried out by adopting a crushing device, wherein the granularity is known to be below 10 mm.
In the primary flotation according to the invention, a heavy medium flotation technique is used, the suspension medium consisting of water and a heavy medium, the heavy medium here being of greater density relative to water, preferably ore fines, such as iron ore. After one flotation, the ash content of the coal can be reduced, but even if the flotation time is prolonged or the operation is repeated, the mass content of the ash is difficult to continue to be reduced to 1.5%. The invention can further reduce the ash content by combining secondary grinding with secondary floatation and magnetic separation. Wherein the secondary flotation can be performed by adopting a conventional flotation process, namely adding water as a medium.
The acid-base treatment is usually used for removing oil in coal, but the alkali treatment and the acid treatment are not used for removing oil, and are mainly used for removing chemically-reactive impurities, so that the ash content is further reduced to be below 1%, and the structural stability and electrochemical activity of the material obtained by subsequent carbonization and carbon coating are ensured.
The carbonization method and the source of the carbon-coated raw material are not particularly limited, as long as the coal material can be carbonized and coated with the carbon material. For example, the carbonization treatment is carried out at a temperature of 1000-2000 ℃ for a time of 1-5 hours; the carbon coating adopts at least one of sugar, asphalt, graphite, polyolefin, phenol and phenol derivatives, the temperature is 500-1000 ℃ and the time is 1-5h. In addition, the carbonization and carbon coating should be kept anaerobic in the calcination system by passing at least one of inert gas, such as nitrogen, and zero group element gas of the periodic table into the calcination system, which will be well known to those skilled in the art and will not be described herein.
The invention breaks up the coated material, and has the effect of dispersing the material, and because the pulverized coal is agglomerated again in the sintering coating process, the pulverized coal is loosely aggregated at the moment and is required to be crushed to a proper particle size, and the D90 is generally smaller than 20um, so that the processing and the performance of the battery are ensured.
Preferred embodiments of the present invention will be described in more detail below. While the preferred embodiments of the present invention are described below, it should be understood that the present invention may be embodied in various forms and should not be limited to the embodiments set forth herein. The specific techniques or conditions are not identified in the examples and are performed according to techniques or conditions described in the literature in this field or according to the product specifications. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention. In the examples below, "%" refers to weight percent, unless explicitly stated otherwise.
The test methods used below included:
the ash content detection method is carried out by referring to GB212-2008 industrial analysis method of coal;
testing of the battery: adopts a button cell: polyvinylidene fluoride PVDF is used as a binder, N-methyl pyrrolidone is used as a solvent, and pole pieces are manufactured; metallic lithium/sodium is the counter electrode; the electrolyte is carbonate as solvent, lithium hexafluorophosphate/sodium hexafluorophosphate as electrolyte. The voltage range is 0.01-3V, and the multiplying power is 0.1C.
The main materials used below include:
anthracite coal adopted in the examples has ash content of 10% by mass; lignite, the mass content of ash was 15%.
Example 1
The preparation method of the battery anode material comprises the following steps:
(1) Crushing the smokeless coal blocks to below 10mm, sieving, returning to above 10mm, and crushing again to obtain coal particles with the granularity of below 10 mm;
(2) Carrying out primary flotation on coal particles with the particle size of less than 10 mm: mixing coal particles, water and iron ore powder (granularity is 0.5-1 mm) by adopting a heavy medium flotation process, wherein the mass ratio of the coal particles, the water and the iron ore powder is as follows: 10:40:20, adopting a heavy medium flotation machine to process, collecting target materials, and carrying out magnetic separation and dehydration to obtain primary flotation coal particles, wherein the ash content is 3%;
(3) Crushing the primary flotation coal particles to D90<10um to obtain coal dust;
(4) Carrying out secondary flotation on the pulverized coal, wherein the secondary flotation is the same as the primary flotation, and carrying out magnetic separation on a flotation liquid obtained by flotation to obtain the pulverized coal, wherein the ash content of the pulverized coal is 1%;
(5) And (3) carrying out alkali treatment and acid treatment on the coal dust, wherein the alkali treatment and the acid treatment comprise aqueous solution of sodium hydroxide with the mass concentration of 10%, slightly boiling for 1h, and washing until the pH value is less than 8.5. Then soaking for 24 hours by adopting sulfuric acid aqueous solution with the mass concentration of 10 percent, and washing with water until the pH value is more than 5.5. Repeating the alkali treatment and the acid treatment for 1-2 times to obtain the coarse material with ash content of 0.6%;
(6) Carbonizing the coarse material in a protective atmosphere, and preserving heat for 2 hours at 1500 ℃ under the protection of nitrogen to obtain carbonized material;
(7) Carbon coating is carried out on the carbonized material, asphalt is used as a coating material, asphalt accounting for 8 percent of the total weight of the carbonized material is added for co-heating, and heating is carried out for 3 hours at 1000 ℃ to obtain the coating material;
(8) And scattering the coating material, specifically adopting an air current crushing mode to disperse the coating material, and sieving the coating material with a 200-mesh sieve to obtain the battery anode material.
The negative electrode material prepared in example 1 was prepared into an electrode, and the electrode was assembled into lithium ion and sodium ion coin cells, respectively, for performance testing. As shown in FIG. 1, the lithium ion battery and the sodium ion battery show better stability in the charge and discharge process, the specific capacity for the first charge is 300.75mAh/g and 278.58mAh/g respectively, and the capacity is not basically attenuated after 10 times of circulation.
Example 2
The preparation method of the battery anode material comprises the following steps:
(1) Crushing lignite coal blocks to below 10mm, sieving, returning to above 10mm, and crushing again to obtain coal particles with the granularity of below 10 mm;
(2) Carrying out primary flotation on coal particles with the particle size of less than 10 mm: mixing coal particles, water and iron ore powder (granularity is 0.5-1 mm) by adopting a heavy medium flotation process, wherein the mass ratio of the coal particles, the water and the iron ore powder is as follows: 10:30:20, treating by adopting a heavy medium flotation machine, collecting a target material, and carrying out magnetic separation and dehydration to obtain primary flotation coal particles, wherein the ash content is 5%;
(3) Crushing the primary flotation coal particles to D90<10um to obtain coal dust;
(4) Carrying out secondary flotation on the pulverized coal, wherein the secondary flotation is the same as the primary flotation, and carrying out magnetic separation on a flotation liquid obtained by flotation to obtain the pulverized coal, wherein the ash content of the pulverized coal is 1.5%;
(5) And (3) carrying out alkali treatment and acid treatment on the coal dust, wherein the coal dust comprises an aqueous solution of sodium hydroxide with the mass concentration of 20%, is slightly boiled for 2 hours, and is washed with water until the pH value is less than 8.5. Then soaking for 24 hours by adopting a sulfuric acid aqueous solution with the mass concentration of 15 percent, and washing with water until the pH value is more than 5.5. Repeating the alkali treatment and the acid treatment for 1-2 times to obtain the coarse material with ash content of 0.8%;
(6) Carbonizing the coarse material in a protective atmosphere, and preserving heat for 2 hours at 1700 ℃ under the protection of nitrogen to obtain carbonized material;
(7) Carbon coating is carried out on the carbonized material, asphalt is used as a coating material, glucose accounting for 5 percent of the total weight of the carbonized material is added for co-heating, and the carbonized material is heated for 3 hours at 800 ℃ to obtain the coating material;
(8) And scattering the coating material, specifically adopting an air current crushing mode to disperse the coating material, and sieving the coating material with a 200-mesh sieve to obtain the battery anode material.
Example 3
The preparation method of the battery anode material comprises the following steps:
(1) Crushing the smokeless coal blocks to below 10mm, sieving, returning to above 10mm, and crushing again to obtain coal particles with the granularity of below 10 mm;
(2) Carrying out primary flotation on coal particles with the particle size of less than 10 mm: mixing coal particles, water and iron ore powder (granularity is 0.5-1 mm) by adopting a heavy medium flotation process, wherein the mass ratio of the coal particles, the water and the iron ore powder is as follows: 10:35:10, treating by adopting a heavy medium flotation machine, collecting a target material, and carrying out magnetic separation and dehydration to obtain primary flotation coal particles, wherein the ash content is 2.8%;
(3) Crushing the primary flotation coal particles to D90<10um to obtain coal dust;
(4) Carrying out secondary flotation on the pulverized coal, wherein the secondary flotation is the same as the primary flotation, and carrying out magnetic separation on a flotation liquid obtained by flotation to obtain the pulverized coal, wherein the ash content of the pulverized coal is 1.1%;
(5) And (3) carrying out alkali treatment and acid treatment on the coal dust, wherein the coal dust comprises an aqueous solution of sodium hydroxide with the mass concentration of 15%, is slightly boiled for 1h, and is washed with water until the pH value is less than 8.5. Then soaking for 24 hours by adopting a sulfuric acid aqueous solution with the mass concentration of 20 percent, and washing with water until the pH value is more than 5.5. Repeating the alkali treatment and the acid treatment for 1-2 times to obtain the coarse material with ash content of 0.6%;
(6) Carbonizing the coarse material in a protective atmosphere, and preserving the temperature of 1200 ℃ for 2 hours under the protection of nitrogen to obtain carbonized material;
(7) Carbon coating is carried out on the carbonized material, graphite is used as a coating material, asphalt accounting for 8 percent of the total weight of the carbonized material is added for co-heating, and heating is carried out for 3 hours at 600 ℃ to obtain the coating material;
(8) And scattering the coating material, specifically adopting an air current crushing mode to disperse the coating material, and sieving the coating material with a 200-mesh sieve to obtain the battery anode material.
Example 4
The preparation method of the battery anode material comprises the following steps:
(1) Crushing the smokeless coal blocks to below 10mm, sieving, returning to above 10mm, and crushing again to obtain coal particles with the granularity of below 10 mm;
(2) Carrying out primary flotation on coal particles with the particle size of less than 10 mm: mixing coal particles, water and iron ore powder (granularity is 0.5-1 mm) by adopting a heavy medium flotation process, wherein the mass ratio of the coal particles, the water and the iron ore powder is as follows: 10:45:20, treating by adopting a heavy medium flotation machine, collecting a target material, and carrying out magnetic separation and dehydration to obtain primary flotation coal particles, wherein the ash content is 3.5%;
(3) Crushing the primary flotation coal particles to D90<10um to obtain coal dust;
(4) Carrying out secondary flotation on the pulverized coal, wherein the secondary flotation is the same as the primary flotation, and carrying out magnetic separation on a flotation liquid obtained by flotation to obtain the pulverized coal, wherein the ash content of the pulverized coal is 1%;
(5) And (3) carrying out alkali treatment and acid treatment on the coal dust, wherein the coal dust comprises an aqueous solution of sodium hydroxide with the mass concentration of 20%, is slightly boiled for 1h, and is washed with water until the pH value is less than 8.5. Then soaking for 24 hours by adopting a sulfuric acid aqueous solution with the mass concentration of 20 percent, and washing with water until the pH value is more than 5.5. Repeating the alkali treatment and the acid treatment for 1-2 times to obtain the coarse material with ash content of 0.5%;
(6) Carbonizing the coarse material in a protective atmosphere, and preserving heat for 2 hours at 1800 ℃ under the protection of nitrogen to obtain carbonized material;
(7) Carbon coating is carried out on the carbonized material, asphalt is used as a coating material, asphalt accounting for 8 percent of the total weight of the carbonized material is added for co-heating, and heating is carried out for 5 hours at 500 ℃ to obtain the coating material;
(8) And scattering the coating material, specifically adopting an air current crushing mode to disperse the coating material, and sieving the coating material with a 200-mesh sieve to obtain the battery anode material.
Example 5
The preparation method of the battery anode material comprises the following steps:
(1) Crushing the smokeless coal blocks to below 10mm, sieving, returning to above 10mm, and crushing again to obtain coal particles with the granularity of below 10 mm;
(2) Carrying out primary flotation on coal particles with the particle size of less than 10 mm: mixing coal particles, water and iron ore powder (granularity is 0.5-1 mm) by adopting a heavy medium flotation process, wherein the mass ratio of the coal particles, the water and the iron ore powder is as follows: 10:40:20, adopting a heavy medium flotation machine to process, collecting target materials, and carrying out magnetic separation and dehydration to obtain primary flotation coal particles, wherein the ash content is 3%;
(3) Crushing the primary flotation coal particles to D90<10um to obtain coal dust;
(4) Carrying out secondary flotation on the pulverized coal, wherein the secondary flotation is the same as the primary flotation, and carrying out magnetic separation on a flotation liquid obtained by flotation to obtain the pulverized coal, wherein the ash content of the pulverized coal is 1%;
(5) And (3) carrying out alkali treatment and acid treatment on the coal dust, wherein the alkali treatment and the acid treatment comprise aqueous solution of sodium hydroxide with the mass concentration of 10%, slightly boiling for 1h, and washing until the pH value is less than 8.5. Then soaking for 24 hours by adopting sulfuric acid aqueous solution with the mass concentration of 10 percent, and washing with water until the pH value is more than 5.5. Repeating the alkali treatment and the acid treatment for 1-2 times to obtain the coarse material with ash content of 0.6%;
(6) Carbonizing the coarse material in a protective atmosphere, and preserving the temperature for 2 hours at 2000 ℃ under the protection of nitrogen to obtain carbonized material;
(7) Carbon coating is carried out on the carbonized material, asphalt is used as a coating material, asphalt accounting for 8 percent of the total weight of the carbonized material is added for co-heating, and heating is carried out for 5 hours at 800 ℃ to obtain the coating material;
(8) And scattering the coating material, specifically adopting an air current crushing mode to disperse the coating material, and sieving the coating material with a 200-mesh sieve to obtain the battery anode material.
Comparative example 1
Referring to example 1, except that steps (3) and (4) are not included, i.e., primary flotation of coal particles is directly subjected to alkali treatment and acid treatment, specifically, pulverized coal is added to an aqueous solution of 10% sodium hydroxide by mass concentration, micro-boiled for 1h, and washed with water to pH <8.5. Then soaking for 24 hours by adopting a sulfuric acid aqueous solution with the mass concentration of 10%, washing with water until the pH value is more than 5.5, and carrying out heavy medium flotation on the obtained material A: mixing the material A, water and iron ore powder (granularity is 0.5-1. Mm), wherein the mass ratio of the material, water and iron ore powder is as follows: and (2) processing the material by adopting a heavy medium flotation machine at a ratio of 10:40:20, collecting a target material, carrying out magnetic separation and dehydration to obtain a material B, and carrying out ash analysis, wherein the content is 2.4%.
Carbonizing the material B in a protective atmosphere, adopting nitrogen protection, and preserving heat for 2 hours at 1500 ℃ to obtain carbonized material; carbon coating is carried out on the carbonized material, asphalt is used as a coating material, asphalt accounting for 8 percent of the total weight of the carbonized material is added for co-heating, and heating is carried out for 3 hours at 1000 ℃ to obtain the coating material; the coating material is scattered, and particularly, an air current crushing mode is adopted to disperse the coating material, and the coating material is sieved by a 200-mesh sieve, so that the comparative material 1 is obtained.
The comparative material 1 is made into an electrode, and is assembled into a lithium ion button battery, and performance tests are carried out, and charge and discharge experiments show that high ash content can reduce the first charge and discharge of the battery, so that larger impossible capacity damage is generated, and the coulomb efficiency is low. As shown in fig. 2, in the half-cell mode of the lithium ion battery, the gram capacity of the first discharge is 977.78mAh, the gram capacity of the first charge is 312.92mAh, the gram capacity of the second discharge is 315.3mAh, the capacity decays rapidly (as shown in fig. 3), and the charge capacity retention rate after 10 cycles is only 47.2%, which is far lower than the level of the cathode material in the normal industry.
Comparative example 2
Referring to example 1, there is a difference in that step (7) is not included, that is, the carbonized material obtained in step (6) is passed through a 200 mesh sieve to obtain comparative material 2.
The comparative material 2 is made into an electrode, and assembled into a lithium ion button cell for performance test, as shown in fig. 4, the coulombic efficiency of the first charge and discharge is improved by 77.1% from 61.9% compared with that of the uncoated material through coating, which indicates that the coulombic efficiency of the material can be improved through carbon coating.
Comparative example 3
Referring to example 1, the same anthracite block was taken, crushed to D90<10um, and the resulting coal fines were first subjected to alkali treatment and acid treatment, specifically, coal fines were added to an aqueous solution of 10% sodium hydroxide by mass concentration, micro-boiled for 1h, and water washed to pH <8.5. Then soaking for 24 hours by adopting a sulfuric acid aqueous solution with the mass concentration of 10%, washing with water until the pH value is more than 5.5, and carrying out heavy medium flotation on the obtained material A: mixing the material A, water and iron ore powder (granularity is 0.5-1. Mm), wherein the mass ratio of the material, water and iron ore powder is as follows: and (2) processing the materials in a ratio of 10:40:20 by adopting a heavy medium flotation machine, collecting target materials, carrying out magnetic separation and dehydration to obtain a material B, and carrying out ash analysis, wherein the content is 3%.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited to the specific details of the above embodiments, and various simple modifications can be made to the technical solution of the present invention within the scope of the technical concept of the present invention, and all the simple modifications belong to the protection scope of the present invention.
In addition, the specific features described in the above embodiments may be combined in any suitable manner without contradiction. The various possible combinations of the invention are not described in detail in order to avoid unnecessary repetition.
Moreover, any combination of the various embodiments of the invention can be made without departing from the spirit of the invention, which should also be considered as disclosed herein.
Claims (10)
1. A preparation method of a battery cathode material is characterized by comprising the following steps: the method comprises the following steps:
(1) Obtaining coal particles with the granularity of less than 10 mm;
(2) Subjecting the coal particles to primary flotation: mixing the coal particles, water and heavy media, adopting a heavy media flotation machine to process, collecting target materials, carrying out primary magnetic separation, and dehydrating to obtain primary flotation coal particles;
(3) Crushing the primary flotation coal particles to obtain coal dust;
(4) Performing secondary flotation on the pulverized coal, and performing secondary magnetic separation on a flotation liquid obtained by flotation to obtain the pulverized coal;
(5) Performing alkali treatment and acid treatment on the pulverized coal to obtain coarse materials;
(6) Carbonizing the coarse material in a protective atmosphere to obtain carbonized material;
(7) Carbon coating is carried out on the carbonized material in a protective atmosphere to obtain a coated material;
(8) And scattering and sieving the coating material to obtain the battery anode material.
2. The method for preparing a battery anode material according to claim 1, wherein: in the step (1), coal is used as a raw material, and the raw material comprises at least one of coking coal, gas coal, lignite, anthracite, long flame coal and lean coal, wherein the mass content of ash in the coal is 5-20%.
3. The method for producing a battery anode material according to claim 2, characterized in that: the mass ratio of the coal particles, the water and the heavy medium in the step (2) is as follows: 10-30:30-50:10-25, preferably 10-20:30-40:10-20 parts of a base; preferably, the heavy medium is iron ore powder; the mass content of ash in the primary flotation coal particles obtained through primary flotation is 1.5-5%.
4. The method for producing a battery anode material according to claim 3, wherein: in the step (3), the powder is crushed until D90 is less than 10um.
5. The method for producing a battery anode material according to any one of claims 1 to 4, characterized in that: the ash content of the pulverized coal in the step (4) is 0.8-1.5% by mass;
optionally, the secondary flotation uses water as a medium.
6. The method for preparing a battery anode material according to claim 5, wherein: in the step (5), an alkaline aqueous solution with the concentration of 5-80wt% is adopted for the alkaline treatment, the pulverized coal and the alkaline aqueous solution are mixed and then are subjected to heating treatment, and then the mixture is filtered and washed until the pH value is less than 8.5; the acid treatment adopts an acidic aqueous solution with the concentration of 0.1-30wt%, and the pH value is more than 5.5 after soaking, filtering and washing;
preferably, the alkali treatment and the acid treatment are repeated 1-2 times, and the ash content of the coarse material obtained through the alkali treatment and the acid treatment is 0.2-0.8% by mass.
7. The method for producing a battery anode material according to any one of claims 1 to 4, characterized in that: the carbonization treatment temperature in the step (6) is 600-2000 ℃ and the time is 1-5h;
optionally, in the step (7), the carbon is coated by at least one of saccharides, asphalt, graphite, polyolefin, tar and resin, wherein the temperature is 500-1000 ℃ and the time is 1-5h;
optionally, in the step (8), the scattering adopts a jet milling mode, and then the powder is sieved by a 100-300 mesh sieve to obtain the battery cathode material.
8. A battery anode material prepared by the method for preparing a battery anode material according to any one of claims 1 to 7.
9. An electrode comprising the battery anode material of claim 1.
10. A battery comprising the electrode of claim 9.
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