GB2623150A - Preparation method for hard carbon negative electrode material, and use of preparation method - Google Patents
Preparation method for hard carbon negative electrode material, and use of preparation method Download PDFInfo
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- GB2623150A GB2623150A GB2310005.0A GB202310005A GB2623150A GB 2623150 A GB2623150 A GB 2623150A GB 202310005 A GB202310005 A GB 202310005A GB 2623150 A GB2623150 A GB 2623150A
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- starch
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- hard carbon
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- 229910021385 hard carbon Inorganic materials 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000007773 negative electrode material Substances 0.000 title abstract 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 56
- 229920002472 Starch Polymers 0.000 claims abstract description 41
- 235000019698 starch Nutrition 0.000 claims abstract description 41
- 239000008107 starch Substances 0.000 claims abstract description 41
- 239000004005 microsphere Substances 0.000 claims abstract description 36
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 36
- 238000010438 heat treatment Methods 0.000 claims abstract description 35
- 235000013808 oxidized starch Nutrition 0.000 claims abstract description 25
- 239000001254 oxidized starch Substances 0.000 claims abstract description 25
- 239000002245 particle Substances 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 18
- 238000003763 carbonization Methods 0.000 claims abstract description 17
- 239000012298 atmosphere Substances 0.000 claims abstract description 13
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 13
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000000926 separation method Methods 0.000 claims abstract description 12
- 230000008569 process Effects 0.000 claims abstract description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000001301 oxygen Substances 0.000 claims abstract description 8
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 239000010405 anode material Substances 0.000 claims description 31
- 238000010926 purge Methods 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 11
- 230000003647 oxidation Effects 0.000 abstract description 6
- 238000007254 oxidation reaction Methods 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 6
- 238000003860 storage Methods 0.000 abstract description 6
- 125000004430 oxygen atom Chemical group O* 0.000 abstract description 2
- 230000002441 reversible effect Effects 0.000 abstract description 2
- 235000012239 silicon dioxide Nutrition 0.000 abstract 4
- 239000005543 nano-size silicon particle Substances 0.000 abstract 2
- 238000005245 sintering Methods 0.000 abstract 2
- 230000000903 blocking effect Effects 0.000 abstract 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- 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 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 229910052708 sodium Inorganic materials 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 230000007547 defect Effects 0.000 description 5
- 238000010586 diagram Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 3
- 239000006260 foam Substances 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- -1 dimethyl vinyl Chemical group 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical class [Fe+2].[Fe+2].[Fe+2].[Fe+3].[Fe+3].[Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCYOBGZUOMKFPA-UHFFFAOYSA-N 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 230000004001 molecular interaction Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- 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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- 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)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
Disclosed are a preparation method for a hard carbon negative electrode material, and a use of the preparation method. The method comprises: mixing starch and nano silicon dioxide, and performing heat treatment on an obtained mixed material at 150-240°C under an inert atmosphere; performing heat treatment on an obtained primary sintering product at 180-220°C under an oxide-containing atmosphere; performing cyclone separation on an obtained secondary sintering product to remove nano silicon dioxide to obtain pre-oxidized starch-based microspheres; and performing carbonization treatment on the pre-oxidized starch-based microspheres under the inert atmosphere to obtain the hard carbon negative electrode material. The silicon dioxide particles of the present invention can be adsorbed on the surface of a starch raw material; in the heat treatment process, starch molecular chains are cross-linked; under the blocking of silicon dioxide, starch particles are not cross-linked and fused, and a spherical structure is formed; and in the pre-oxidation process, oxygen vacancies generated after introduced oxygen atoms are carbonized increase active sites for sodium ion storage, thereby improving the reversible capacity of a sodium-ion battery.
Description
METHOD OF PREPARING HARD CARBON ANODE MATERIAL AND USE
THEREOF
FIELD
[0001] The present application relates to the technical field of anode materials for batteries, in particular to a method of preparing a hard carbon anode material and use of the same.
BACKGROUND
[0002] With the rapid development of mobile electronic devices, grid energy storage and electric vehicles, Li-ion batteries have occupied a central position in the new energy market.
Although lithium-ion batteries (LiBs) are currently the most compatible requirements with practical application, the nascent sodium-ion batteries (SiBs) are gradually becoming a solution to replace lithium-ion batteries, considering the scarcity and limitation of lithium resources. Sodium and lithium have similar physicochemical properties, and sodium is highly abundant in nature and the price is inexpensive. In summary sodium is currently the most desirable element to replace lithium in rechargeable batteries for energy storage systems, and advanced electrode materials are the key to developing sodium ion batteries.
[0003] In the past few years, many excellent positive electrode materials tiw SiBs, such as layered transition metal oxides, polyphosphate compounds and Prussian blue analogues, have been developed. However, in terms of anode material selection, graphite anode used for commercialization of lithium-ion batteries are not sufficient for sodium storage. Therefore, the development of excellent anode materials has become the most serious challenge for applications of sodium ion battery. Among the most promising directions so far, hard carbon has sufficient sodium storage sites and has been identified as the preferred anode material for commercial sodium ion batteries (SiBs).
[0004] However, the hard carbon anode materials reported in the prior art still suffer from low first efficiency, low capacity complex production process, and high production cost, which seriously limit the development and commercial application of sodium ion batteries.
SUMMARY
[0005] The purpose of the present application is to solve at least one of the technical problems of the prior art described above. to this end, the present application provides a method of preparing a hard carbon anode material and use of the same.
[0006] According to one aspect of the present application, a method of preparing a hard carbon anode material is provided, comprising the following steps: Si: mixing starch with nano-silica, and performing heat treatment on the obtained mixture at 150°C to 240°C under an inert atmosphere to obtain a first-sintered product; S2: performing heat treatment on the first-sintered product at I 80°C to 220°C under an oxygen-containing atmosphere to obtain a second-sintered product; S3: cyclonically separating the second-sintered product to remove the nano-silica, to obtain pre-oxidized starch-based microspheres; and S4: performing carbonization treatment on the pre-oxidized starch-based microspheres under an inert atmosphere to obtain the hard carbon anode material.
[0007] In some embodiments of the present application, in step Si, the starch has a particle size of 2um to 80m, and the nano-silica has a particle size of 5mia to 50mn. Further, the nano-silica may be fumed silica.
[0008] In some embodiments of the present application, in step Si, a mass ratio of the starch to the nano-silica is 100: (0.5-I 0).
[0009] In some embodiments of the present application, in step Si, the heat treatment is performed for 3h to 20h.
[0010] In some embodiments of the present application, in step Si, the temperature is raised to a target temperature of the heat treatment at a rate of 0.5°C/min to I 5°C/min.
[0011] In some embodiments of the present application, the heat treatment in step S2 is: placing the first-sintered product in a reaction device, introducing oxygen-containing gas to purge for 30min to 120min, and then heating up to a target temperature for heat treatment.
Further, the temperature is raised to the target temperature of the heat treatment at a rate of 0.5°C/min to I 0°C/min.
[0012] In some embodiments of the present application, in step S2, the heat treatment is performed for 4h to 24h.
[0013] In some embodiments of the present application, in step S3, the pre-oxidized starch-based microspheres obtained after the cyclone separation are cyclonically separated again, and the cyclone separation is repeated 2 times to 8 times according to the above process.
[0014] In some embodiments of the present application, in step S4, the carbonization treatment is performed at a temperature of 1000°C to 1600°C. Further, the temperature is raised to the target temperature of the carbonization treatment at a rate of 0.5°C/minto I 0°C/min.
[0015] In some embodiments of the present application, in step S4, the carbonization treatment is: placing the pre-oxidized starch-based microspheres in a high-temperature carbonization furnace, introducing inert gas to purge for 30min to 120min, and then heating up to a target temperature for carbonization treatment.
[0016] In some embodiments of the present application, in step S4, the carbonization treatment is performed for lh to 5h.
[0017] In some embodiments of the present application, the hard carbon anode material has a specific surface area of 2m2/g to 4m2/g and a particle size D50 of 5p.m to lOpm.
[0018] The present application further provides use of the above preparation method in the preparation of sodium ion batteries.
[0019] According to a preferred embodiment of the present application, it has at least the following beneficial effects.
[0020] 1. In the present application, by simply mixing starch with nano-silica, the silica particles can be easily adsorbed on the surface of the starch material, forming a structure similar to "micelles". During the heat treatment process, the hydrogen bond between the starch molecules breaks to form an ether bond, which results in cross-linking between the starch molecule chains, but under the barrier of silica, the starch particles do not cross-link and fuse, -3 -and the raw material molecules form a spherical structure with less surface energy through molecular rearrangement. On the contrary if silica is not added, the pure starch raw material particles lack molecular interaction with silica particles, which makes the raw material molecules flow easily and fuse with other molecules, generating a pile-like product with less surface energy -foam carbon, which is easy to make the SEI film increase and lead to the problem of lower specific capacity and first efficiency.
[00211 2. In the present application, the raw material is pre-oxidized, and the C=0 bond or C-0 bond is generated during the pre-oxidation process, and the oxygen vacancies generated by the introduction of oxygen atoms after carbonization increase the active sites for sodium ion storage, thus increasing the reversible capacity of sodium ion batteries. In addition, there are some pores on the surface of the starch powder itself, and after pre-oxidation, the oxygen molecules involved in the reaction will fill some larger pores, thus reducing the defects and playing a repairing effect, and reducing the specific surface area of the hard carbon material.
[0022] 3. In the present application, the pre-oxidized starch-based microspheres and silica are separated by a simple cyclone separation method, the separation process is simple and the separation effect is remarkable.
[00231 4. The present application has less process steps, simple process, low energy consumption, high degree of operation, and low production cost, which is friendly to the environment and suitable for large-scale production.
BRIEF DESCRIPTION OF THE DRAWINGS
[0024] The present application is further described below in conjunction with the accompanying drawings and examples.
I-00251 Figure 1 is an SEM diagram of a hard carbon anode material prepared according to Example I of the present application; 1-00261 Figure 2 is an XRD diagram of the hard carbon anode material prepared according to Example 1 of the present application; and -4 - [0027] Figure 3 is the charging and discharging curve of the hard carbon anode material prepared according to Example 1 of the present application.
DETAILED DESCRIPTION
[0028] The following will be a clear and complete description of the conception of the present application and the technical effects produced in conjunction with the examples, in order to fully understand the purpose, features and effects of the present application. Apparently, the described examples are only a part of the examples of the present application, not all of them. Based on the examples of the present application, other examples obtained by a person skilled in the art without creative labor fall within the scope of protection of the present application.
Example I
[0029] A hard carbon anode material was prepared according to the present example, which comprised the following steps.
[0039] (I) Starch with a particle size of 2um to 80um and nano-silica (5nm to 50nm) were mixed at a mass ratio of 100:0.5 in a high-speed mixer for 5 minutes to obtain the mixed starch.
[0031] (2) The starch mixed with nano-silica obtained from step (1) was placed into a tube furnace and heated up to 220°C at a heating rate of 5°C/min under the protection of NI, thermostatically heat treated for 81i, and cooled down to room temperature to obtain a first-sintered product.
[0032] (3) The starch-based microspheres obtained from step (2) were placed into a tube furnace, purged by introducing air for 30min, and continued to be heated up to the target temperature of 200°C at a heating rate of 5°C/min after 30min of purging, thermostatically heat treated at the target temperature for 12h, and cooled down to room temperature to obtain a second-sintered product mixed with nano-silica.
[0033] (4) The second-sintered product obtained from step (3) was separated through a cyclone separator to obtain silica and pre-oxidized starch-based microspheres, and the _ s _ pre-oxidized starch-based microspheres were further separated by cyclone separation for 2 times to remove silica from the pre-oxidized starch-based microspheres, to obtain pre-oxidized starch-based microspheres with a purity of 99.7%.
100341 (5) The pre-oxidized starch-based microspheres obtained in step (4) were placed into a high-temperature carbonization furnace, purged by introducing N, for 30min, heated up to the target temperature of 1400°C at a heating rate of 5"C/min, and thermostatically heat treated at the target temperature and under N, atmosphere tbr 2h to remove the oxygen-containing functional groups and bound water in the material, in which the structure is further rearranged, and cooled down to room temperature to obtain the hard carbon anode material.
r00351 Figure 1 shows the SEM diagram of the hard carbon anode material prepared according to Example I, from which it can be seen that the material morphology was spheroid particles with rounded edges.
100361 Figure 2 shows the XRD diagram of the hard carbon anode material prepared according to Example I, from which it can be seen that about 24° was corresponding to the diffraction peak (002) crystal plane, the half-peak width was larger and the angle was smaller, indicating that the disorder of this hard carbon material was higher, and the calculated Layer spacing d=0.37 mu was favorable for the storage and release of sodium ions.
Example 2
100371 A hard carbon anode material was prepared according to the present example, which comprised the following steps.
100381 (I) Starch with a particle size of 2pm to 80pm and nano-silica (5nm to 50nm) were mixed at a mass ratio of 100:1 in a high-speed mixer for 5 minutes to obtain the mixed starch.
100391 (2) The starch mixed with nano-silica obtained from step ( I) was placed into a tube furnace and heated up to 220°C at a heating rate of 5°C/min under the protection of N,, thermostatically heat treated for 8h, and cooled down to room temperature to obtain a first-sintered product.
100401 (3) The starch-based microspheres obtained from step (2) were placed into a tube furnace, purged by introducing air for 30min, and continued to be heated up to the target -6 -temperature of 200°C at a heating rate of 5°C/min after 30min of purging, thermostatically heat treated at the target temperature for 12h, and cooled down to room temperature to obtain a second-sintered product mixed with nano-silica.
[0041] (4) The second-sintered product obtained from step (3) was separated through a cyclone separator to obtain silica and pre-oxidized starch-based microspheres, and the pre-oxidized starch-based microspheres were further separated by cyclone separation for 4 times to remove silica from the pre-oxidized starch-based microspheres, to obtain pre-oxidized starch-based microspheres with a purity of 99.6%.
[00421 (5) The pre-oxidized starch-based microspheres obtained in step (4) were placed into a high-temperature carbonization furnace, purged by introducing N, for 30min, heated up to the target temperature of 1400°C at a heating rate of 5°C/min, and thermostatically heat treated at the target temperature and under N2 atmosphere for 2h, and cooled down to room temperature to obtain the hard carbon anode material.
Example 3
[0043] A hard carbon anode material was prepared according to the present example, which comprised the following steps.
[0044] (1) Starch with a particle size of 2iim to 800m and nano-silica (5nm to 50nni) were mixed at a mass ratio of 100:3 in a high-speed mixer for 5 minutes to obtain the mixed starch.
[0045] (2) The starch mixed with nano-silica obtained from step (1) was placed into a tube 20 furnace and heated up to 220°C at a heating rate of 5°C/min under the protection of NI, thermostatically heat treated for 811, and cooled down to room temperature to obtain a first-sintered product.
[0046] (3) The starch-based microspheres obtained from step (2) were placed into a tube furnace, purged by introducing air for 30min, and continued to be heated up to the target temperature of 200°C at a heating rate of 5°C/min after 30min of purging, thermostatically heat treated at the target temperature tor 12h, and cooled down to room temperature to obtain the second-sintered product mixed with nano-silica.
[0047] (4) The second-sintered product obtained from step (3) was separated through a cyclone separator to obtain silica and pre-oxidized starch-based microspheres, and the pre-oxidized starch-based microspheres were further separated by cyclone separation for 6 times to remove silica from the pre-oxidized starch-based microspheres, to obtain pre-oxidized starch-based microspheres with a purity of 99.5%.
[0048] (5) The pre-oxidized starch-based microspheres obtained in step (4) were placed into a high-temperature carbonization furnace, purged by introducing N, for 30min, heated up to the target temperature of 1400°C at a heating rate of 5°C/min, and thermostatically heat treated at the target temperature and under NI atmosphere for 2h, and cooled down to room temperature to obtain the hard carbon anode material.
Contrast example 1
[00491 A hard carbon anode material was prepared according to the present contrast example, which differed from Example 1 in that no nano-silica was added. The specific process was as [0050] (1) Starch with a particle size of 2pm to 80ftm was taken as a raw material, placed into a tube furnace, heated up to 220°C with a heating rate of 5°C/min under the protection of N,, thermostatically heat treated for 8h, and cooled down to room temperature to obtain a lumpy first-sintered material.
[0051] (2) The lumpy first-sintered material obtained from step (1) was crushed into particles of 4um to 7pm, purged by introducing air lift 30min, and continued to he heated up to the target temperature of 200°C at a heating rate of 5°C/min after 30min of purging, thermostatically heat treated at the target temperature for 12h, and cooled down to room temperature, to obtain the pre-oxidized lumpy second-sintered material.
[00521 (3) The pre-oxidized lumpy second-sintered material obtained from step (2) was crushed into particles of 4pm to 7pm, placed into a high-temperature carbonization furnace, purged by introducing N, for 30min, heated up to the target temperature of 1400°C at a heating rate of 5°C/min, and thermostatically heat treated at the target temperature and under NI atmosphere for 2h, and cooled down to room temperature, to obtain the hard carbon anode material. -8 -
Contrast example 2
[0053] A hard carbon anode material was prepared according to the present contrast example, which differed from Example I in that no pre-oxidation was carried out. The specific process was as following.
[0054] (1) Starch with a particle size of 2m to 80pm and nano-silica (5nm to 50nm) were mixed at a mass ratio of 100:0.5 in a high-speed mixer for 5 minutes to obtain the mixed starch.
[0055] (2) The starch mixed with nano-silica obtained from step ( I) was placed into a tube furnace and heated up to 220°C at a heating rate of 5°C/min under the protection of 1'41, thermostatically heat treated for 8h, and cooled down to room temperature to obtain a first-sintered starch-based microspheres.
[0056] (3) The first-sintered starch-based microspheres obtained from step (2) were separated through a cyclone separator to obtain silica and starch-based microspheres, and the starch-based microspheres were further separated by cyclone separation for 2 times to remove silica from the starch-based microspheres, to obtain starch-based microspheres with a purity of 99.4%.
[0057] (4) The starch-based microspheres obtained in step (3) were placed into a high-temperature carbonization furnace, purged by introducing N, for 30min, heated up to the target temperature of 1400°C at a heating rate of 5°C/min, and thermostatically heat treated at the target temperature and under N, atmosphere for 2h, and cooled down to room temperature to obtain the hard carbon anode material.
Physicochemical properties [0058] Table 1 shows the comparison of the specific surface area of the samples prepared according to Example 1, 2 and 3 and Contrast example 1 and 2. In Contrast example 1, no fluxing with nano-silica was performed, the fusion between the material particles occurred during the first and second sintered process, thus producing lumpy carbon or even foam carbon.
In order to prepare into a powder, the lumpy carbon or the foam carbon needs to be crushed repeatedly, and this will cause defects on the surface of the material particles during the crushing process, thus increasing the specific surface area. The difference between Contrast example 2 and Example 1 was that the starch-based microspheres after the first-sintered were not pre-oxidized and were directly carbonized at high temperature, and some defects of the powder were not repaired in the absence of pre-oxidation treatment, and the specific surface area of the corresponding finished product was larger than that of the pre-oxidized product.
Table 1 Particle size and specific surface area test data of the hard carbon anode materials according to the examples and the samples according to the contrast examples Sample Particle size D50 (nm) Specific surface area (m2/g)
Example 1 8.51 3.53
Example 2 7.98 2.93
Example 3 8.58 2.68
Contrast example 1 5.25 11.27 Contrast example 2 8.13 23.35
Test example
1100591 The samples prepared according to Example 1, 2 and 3 and Contrast example 1 and 2 were respectively assembled into a button cell to test the electrochemical properties of the samples. The positive electrode of the cell was sodium flake, the anode of the cell was all active material, the ratio of the anode material was active material (90% by volume), acetylene black (5% by volume), polyvinylidene fluoride (5% by volume) (PVDF), flpVDF:NMP (N-methylpyrrolidone) = 1: 10, the solvent was a triple system of EC (ethylene carbonate), DMC (dimethyl vinyl carbonate) and EMC (methyl ethyl carbonate), the electrolyte was a solution with LiPF6 concentration of I mol/L (where the volume ratio of EC, DMC and EMC was 1:1:1), and the button cell was prepared in a glove box filled with argon gas. The cell charge and discharge tests were performed on the LAND battery system with a charge and discharge voltage range of 0 to 2 V. The test results are shown in Table 2.
Table 2 Electrochemical performance test data of the hard carbon anode materials according to the examples and the samples according to the contrast examples Sample 0.05C discharge specific capacity Coulomb efficiency Capacity retention of 200 cycles (mAh/g) (%) ( % ) Example 1 329.3 86.75 91 Example 2 326.8 86.23 91 Example 3 323.7 85.94 90 Contrast example 1 313.3 84.55 88 Contrast example 2 270.6 76.9 82 [0060] As can be seen from Table 2, the electrochemical performance of contrast example 1 is somewhat worse than that of the examples, which is due to the generation of lumpy or foamy carbon during the preparation process, the defects caused to the powder during the crushing treatment, and the increase in the specific surface area of the prepared hard carbon product leading to the increase in the SE1 film, which leads to a decrease in the specific capacity and first efficiency. In contrast example 2, the sample was carbonized directly without pre-oxidation treatment, which lacked sodium ion storage active sites and defects were not effectively repaired compared to the pre-oxidized material, resulting in a significant decrease in specific capacity, first efficiency and cycling performance.
[0061] The examples of the present application are described in detail above in conjunction with the accompanying drawings, but the present application is not limited to the above examples, and various variations can be made within the scope of knowledge possessed by a person of ordinary skill in the art to which they belong without departing from the purpose of the present application. In addition, the examples of the present application and the features in the examples can be combined with each other without conflict.
Claims (10)
- CLAIMSI. A method of preparing a hard carbon anode material, comprising the following steps: Si: mixing starch with nano-silica, and performing heat treatment on the obtained mixture at I 50°C to 240°C under an inert atmosphere to obtain a first-sintered product; S2: performing heat treatment on the first-sintered product at 180°C to 220°C under an oxygen-containing atmosphere to obtain a second-sintered product; S3: cyclonically separating the second-sintered product to remove the nano-silica, to obtain pre-oxidized starch-based microspheres; and JO 54: performing carbonization treatment on the pre-oxidized starch-based microspheres under an inert atmosphere to obtain the hard carbon anode material.
- 2. The preparation method according to claim 1, wherein, in step Si, the starch has a particle size of 2ilin to 50mm, and the nano-silica has a particle size of 5nm to 50nm.
- 3. The preparation method according to claim 1, wherein, in step Si, a mass ratio of the starch to the nano-silica is 100: (0.5-10).
- 4. The preparation method according to claim 1, wherein, in step Si, the heat treatment is 20 performed for 3h to 20h.
- 5. The preparation method according to claim I, wherein the heat treatment in step S2 is: placing the first-sintered product in a reaction device, introducing oxygen-containing gas to purge for 30min to I 20min, and then heating up to a target temperature for heat treatment.
- 6. The preparation method according to claim 1, wherein, in step S2, the heat treatment is -12 -performed for 4h to 24h.
- 7. The preparation method according to claim 1, wherein, in step S3, the pre-oxidized starch-based microspheres obtained after the cyclone separation are cyclonically separated again, and the cyclone separation is repeated 2 times to 8 times according to the above process.
- 8. The preparation method according to claim 1, wherein, in step S4, the carbonization treatment is performed at a temperature of 1000°C to 1600°C.
- 9. The preparation method according to claim 1, wherein, in step S4, the carbonization treatment is performed for lh to 5h.
- 10. Use of the preparation method according to any one of claims 1 to 9 in the preparation of sodium ion batteries.
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| CN114436237A (en) * | 2021-12-21 | 2022-05-06 | 华中科技大学 | Hard carbon material and preparation method and application thereof |
| CN114988391A (en) * | 2022-06-29 | 2022-09-02 | 宜昌邦普循环科技有限公司 | Preparation method and application of hard carbon negative electrode material |
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- 2022-09-09 DE DE112022000467.3T patent/DE112022000467T5/en active Pending
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| JP2004220972A (en) * | 2003-01-16 | 2004-08-05 | Hitachi Chem Co Ltd | Carbon material for lithium secondary battery negative electrode and manufacture thereof, lithium secondary battery negative electrode and lithium secondary battery |
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