CN116741992B - Porous hard carbon material and preparation method thereof, negative electrode plate and sodium ion battery - Google Patents
Porous hard carbon material and preparation method thereof, negative electrode plate and sodium ion battery Download PDFInfo
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- CN116741992B CN116741992B CN202310592823.7A CN202310592823A CN116741992B CN 116741992 B CN116741992 B CN 116741992B CN 202310592823 A CN202310592823 A CN 202310592823A CN 116741992 B CN116741992 B CN 116741992B
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- 229910021385 hard carbon Inorganic materials 0.000 title claims abstract description 78
- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 62
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 49
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000011734 sodium Substances 0.000 claims abstract description 22
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 22
- 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 claims abstract description 19
- 239000000843 powder Substances 0.000 claims abstract description 18
- 239000008367 deionised water Substances 0.000 claims abstract description 10
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000007833 carbon precursor Substances 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 9
- 238000005406 washing Methods 0.000 claims abstract description 7
- 238000001914 filtration Methods 0.000 claims abstract description 4
- 238000010000 carbonizing Methods 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 17
- 238000010438 heat treatment Methods 0.000 claims description 15
- 239000011148 porous material Substances 0.000 claims description 15
- 239000012298 atmosphere Substances 0.000 claims description 11
- 238000003763 carbonization Methods 0.000 claims description 9
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 8
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 8
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 8
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 4
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 3
- 229920002472 Starch Polymers 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 239000011229 interlayer Substances 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 claims description 3
- 239000000661 sodium alginate Substances 0.000 claims description 3
- 235000010413 sodium alginate Nutrition 0.000 claims description 3
- 229940005550 sodium alginate Drugs 0.000 claims description 3
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 claims description 3
- 239000008107 starch Substances 0.000 claims description 3
- 235000019698 starch Nutrition 0.000 claims description 3
- 239000000463 material Substances 0.000 abstract description 12
- 238000009776 industrial production Methods 0.000 abstract description 2
- 238000012545 processing Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
- 229910052799 carbon Inorganic materials 0.000 description 7
- 238000003860 storage Methods 0.000 description 7
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 229910001416 lithium ion Inorganic materials 0.000 description 6
- 239000011888 foil Substances 0.000 description 5
- 239000007773 negative electrode material Substances 0.000 description 5
- 239000002243 precursor Substances 0.000 description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 239000006258 conductive agent Substances 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 230000001351 cycling effect Effects 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 238000009830 intercalation Methods 0.000 description 3
- 230000002687 intercalation Effects 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 229910021384 soft carbon Inorganic materials 0.000 description 3
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- 229910003481 amorphous carbon Inorganic materials 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 230000008595 infiltration Effects 0.000 description 2
- 238000001764 infiltration Methods 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 239000011268 mixed slurry Substances 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000013590 bulk material Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 description 1
- 229910001488 sodium perchlorate Inorganic materials 0.000 description 1
- 159000000000 sodium salts Chemical group 0.000 description 1
- 238000009210 therapy by ultrasound Methods 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
- H01M10/054—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
- 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
- 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
Abstract
The application discloses a porous hard carbon material and a preparation method thereof, a negative electrode plate and a sodium ion battery, and belongs to the technical field of battery material processing. The preparation method comprises the following steps: (1) pretreating a hard carbon precursor at a low temperature; (2) Ultrasonically washing the powder subjected to low-temperature pretreatment with deionized water at normal temperature, filtering and drying to obtain sodium carbonate-removed powder; (3) And carbonizing the sodium carbonate-removed powder at high temperature to obtain the porous hard carbon material for the negative electrode of the sodium ion battery. The porous hard carbon material for the negative electrode of the sodium ion battery has the advantages of high specific capacity, good multiplying power performance and stable cycle performance, and is simple in preparation process, wide in raw material source, low in cost and easy to realize large-scale industrial production.
Description
Technical Field
The application relates to a battery anode material and preparation and application thereof, in particular to a porous hard carbon material and preparation and application thereof, belonging to the technical field of new energy secondary battery material processing.
Background
With the explosive growth of new energy automobiles and other market demands on lithium ion batteries, the consumption of lithium resources is continuously increased, so that the price of metal lithium raw materials is rapidly increased, and the search for an alternative solution of the lithium ion battery is particularly important. Compared with lithium resources, the sodium resources are lower in price, the sodium resources in China are abundant in storage and wide in distribution, can support large-scale sustainable development of an industrial chain, have obvious resource advantages, and simultaneously guarantee energy safety in China. In addition, the sodium ion battery has the advantages of higher safety, better low-temperature performance and the like compared with the lithium ion battery, and can be effectively supplemented and replaced in the fields of low-speed electric vehicles, two-wheel vehicles, energy storage and the like in the future.
For thermodynamic reasons, the graphite negative electrode material with the highest commercialization in lithium ion batteries cannot be used in sodium ion batteries, and at present, amorphous carbon represented by hard carbon and soft carbon is the main choice of the negative electrode material of the sodium ion batteries, wherein the sodium storage capacity of the hard carbon is superior to that of the soft carbon, and the lithium ion batteries have extremely strong commercialization potential. Compared with lithium ions, sodium ions have larger atomic radius and relative atomic mass, the sodium ions slowly diffuse in the battery electrode material, and the conductivity of the hard carbon material is lower than that of soft carbon, so that the hard carbon material has the problems of large irreversible capacity loss, poor rate performance and the like. The construction of the porous structure is a method for effectively improving the rate capability and capacity, and abundant defect sites exist in the porous carbon, and the defect sites can become active sites for sodium storage and improve the sodium storage capacity; and secondly, the porous structure of the porous carbon can effectively shorten the diffusion and conduction distance of sodium ions and electrons in the material, improve charge transfer kinetics, improve conductivity and finally improve the cycle stability and rate capability of the sodium ion battery. Finally, the internal space structure of the porous carbon can effectively buffer the volume expansion during sodium intercalation, and the cycling stability of the sodium ion battery is improved.
Currently, porous carbon materials can be obtained by reactive etching of strong bases with carbon at high temperatures, such as potassium hydroxide pore formers, but etching of carbon by potassium hydroxide can result in reduced final yields of carbon materials. Meanwhile, a large amount of acid is needed for removing potassium after etching and pore-forming are completed, and environmental pollution is caused. Therefore, the development of a simple, economical and environment-friendly method for preparing the porous carbon anode material has important significance.
Disclosure of Invention
The invention aims to overcome the defects of low yield and large environmental pollution existing in the prior art that pore formers, etchants and the like are needed for preparing porous carbon materials, and provides a porous hard carbon material for a sodium ion battery cathode. The invention further aims to provide a preparation method of the porous hard carbon material for the negative electrode of the sodium ion battery.
In order to achieve the above object, the present invention provides the following technical solutions:
a porous hard carbon material for a sodium ion battery cathode, wherein the interlayer spacing of the porous hard carbon material is 0.36-0.39 nm.
The porous hard carbon material structurally comprises micropores, mesopores and macropores, wherein the pore diameter of the micropores is less than or equal to 2nm, the pore diameter of the mesopores is 2-50 nm, and the pore diameter of the macropores is more than or equal to 50nm.
The porous hard carbon material is favorable for infiltration of electrolyte, can effectively shorten diffusion and conduction distance of sodium ions and electrons in the material, improves charge transfer dynamics, relieves volume expansion of the material in the charge-discharge process, and improves rate capability and cycle stability of a sodium ion battery.
Another object of the present invention is to provide a preparation process, which realizes the purpose of preparing the porous hard carbon material with low cost and high efficiency through a proper hard carbon heat treatment process.
The preparation method of the porous hard carbon material for the negative electrode of the sodium ion battery comprises the following steps:
(1) Pretreating a hard carbon precursor in an inert atmosphere;
(2) After natural cooling, ultrasonically washing the pretreated powder with deionized water, filtering and drying to obtain sodium carbonate-removed powder;
(3) And carbonizing the powder with the sodium carbonate removed at high temperature in an inert atmosphere to obtain the porous hard carbon material for the negative electrode of the sodium ion battery.
The method is simple, economical and environment-friendly, fully utilizes sodium carbonate salt formed by the precursor in the low-temperature presintering process as a salt template, builds the porous material in situ, and has extremely high porous efficiency due to in-situ growth of the sodium carbonate salt template, uniform and fine original porous dispersion, and finally has stable structure and durable weather resistance of the porous hard carbon obtained by high-temperature carbonization. The finally obtained sodium ion battery anode porous hard carbon material is favorable for infiltration of electrolyte, can effectively shorten diffusion and conduction distance of sodium ions and electrons in the material, improves charge transfer dynamics, relieves volume expansion of the material in the charge and discharge process, and improves rate capability and cycle stability of the sodium ion battery.
Further, in the step (1), the inert atmosphere is one or two of nitrogen and argon.
Further, in the step (1), the hard carbon precursor is a sodium salt containing a natural polymer compound.
Preferably, in the step (1), the hard carbon precursor is at least one of sodium carboxymethyl cellulose, sodium carboxymethyl starch, sodium alginate and sodium polyacrylate.
Further, in the step (1), the pretreatment is preferably performed under low temperature conditions. Preferably, the low temperature is 200-600 ℃. The low temperature is relative to the high temperature carbonization temperature in the subsequent step (3), the pretreatment at 200-600 ℃ is selected to moderately carbonize the precursor material, and conditions are provided for sodium carbonate pore-forming.
In the step (1), the low-temperature pretreatment is to heat up to 200-600 ℃ at a heating rate of 1-5 ℃/min, and the low-temperature pretreatment is to treat for 1-6 hours under an inert atmosphere at constant temperature. Preferably, the low temperature pretreatment temperature is 220-500 ℃. More preferably, the low temperature pretreatment temperature is 250-500 ℃. For example, it may be 300℃and 350 ℃.
Further, in the step (2), the pretreated powder is ultrasonically washed by deionized water at normal temperature.
Further, in the step (2), the mass ratio of the powder to the deionized water is 1: (5-50). And washing with enough deionized water to remove sodium carbonate fully, so that enough micropores in the porous hard carbon and a porous structure with large holes are formed during subsequent high-temperature carbonization treatment, wherein the micropores in the porous hard carbon are enough, and the porous hard carbon has a middle Kong Shiliang structure.
Further, in the step (2), the washing time is 1 to 12 hours. Preferably, the washing time is 1 to 6 hours, or 6 to 10 hours.
In the step (2), the drying mode is vacuum drying, the temperature is 60-120 ℃, and the drying time is 4-16h. Preferably, the drying time is 4 to 12 hours.
In the step (3), the inert atmosphere is one of nitrogen and argon. The inert atmosphere in the step (1) and the step (3) can be the same or different, and mainly the inert atmosphere protection conditions are provided, and the implementation effect is not influenced by the specific inert gas.
Further, in the step (3), the high-temperature carbonization is performed by heating to 900-1500 ℃ at a speed of 1-10 ℃/min and staying for 0.5-8 h.
Preferably, the high temperature carbonization temperature is 1100-1500 ℃. More preferably, the high-temperature carbonization temperature is 1300-1500 ℃, for example 1350 ℃, 1400 ℃, 1450 ℃, etc. can be selected.
According to another aspect of the application, the purpose is to provide a negative electrode plate, wherein the porous hard carbon material for the negative electrode is applied to a sodium ion battery, and the material performance advantage of the porous hard carbon material is exerted by combining the characteristics of the sodium ion battery.
The negative electrode plate contains the porous hard carbon material or the porous hard carbon material prepared by the method.
Namely, the porous hard carbon material is used for manufacturing a negative electrode material.
Further, the negative electrode plate is prepared by coating a mixed slurry containing the porous hard carbon material or the negative electrode material prepared by the method, a conductive agent and a binder on a metal foil, preferably an aluminum foil, carrying out high-temperature treatment and slicing.
Further, in the mixed slurry, the mass ratio of the composite material, the conductive agent and the binder is 7-9: 0.5 to 1.5:0.5 to 1.5.
Specifically, a porous hard carbon material, a conductive agent (Super P) and a binder (CMC) are uniformly ground in a mass ratio of 8:1:1, a small amount of deionized water is added to prepare slurry, the slurry is coated on copper foil or aluminum foil by a film coater, the copper foil or aluminum foil is then subjected to heat preservation in a vacuum drying oven at 100 ℃ for 24 hours, and then the dried electrode sheet is cut into electrode sheets with the diameter of 12mm by a slicer.
According to the application, the application of the negative electrode plate is provided, and the negative electrode plate is applied to the downstream sodium ion battery industry, so that the advantages of simplicity, economy and environmental protection of the negative electrode plate are fully exerted, and the advantages of good cycle stability, low cost and environmental protection are exerted.
A sodium ion half cell or a sodium ion cell comprises the negative electrode plate.
Compared with the prior art, the invention has the beneficial effects that:
1. the preparation method is extremely simple, does not need to add any pore-forming agent or salt template agent, fully utilizes sodium carbonate salt formed by the precursor in the low-temperature presintering process as a salt template, builds the porous material in situ, has wide precursor sources and low cost, and is easy to realize industrial production.
2. The porous hard carbon material of the negative electrode has rich three-dimensional cross-linked pore structure, which is beneficial to effectively shortening the diffusion and conduction distance of sodium ions and electrons in the material, improving charge transfer kinetics, improving conductivity and finally improving the cycling stability and rate capability of the sodium ion battery. And secondly, the internal space structure of the porous carbon can effectively buffer the volume expansion during sodium intercalation, so that the cycling stability of the sodium ion battery is improved.
3. The porous hard carbon material prepared by the invention is applied to sodium ion batteries/sodium ion half batteries, has the characteristics of high specific capacity, good rate capability and stable cycle performance, and has important significance for commercial application of sodium ion batteries.
Drawings
Fig. 1 is an XRD pattern of the porous hard carbon material of example 1.
FIG. 2 is a scanning electron microscope image of the porous hard carbon material of example 1.
Fig. 3 is a scanning electron microscope view (enlarged view) of the porous hard carbon material of example 1.
Fig. 4 is a charge-discharge graph of the porous hard carbon material of example 1.
Detailed Description
The present invention will be described in further detail with reference to test examples and specific embodiments. It should not be construed that the scope of the above subject matter of the present invention is limited to the following embodiments, and all techniques realized based on the present invention are within the scope of the present invention.
Example 1
Preparation of porous hard carbon material 1# sample
Step (1): 10g of sodium carboxymethylcellulose (hard carbon precursor) was placed in a tube furnace, and heat-treated for 2 hours at a temperature-rising rate of 2 ℃/min to 300 ℃ (pretreatment temperature) under a nitrogen atmosphere.
Step (2): after natural cooling, grinding the powder pretreated at low temperature into powder by using a mortar, placing the powder into a beaker, adding 200mL of deionized water, performing ultrasonic treatment at normal temperature for 2 hours, filtering, and drying in a vacuum drying oven at 100 ℃ for 12 hours to obtain the powder with sodium carbonate removed.
Step (3): and (3) placing the sodium carbonate-removed powder in a tube furnace, heating to 1400 ℃ at a heating rate of 2 ℃/min under nitrogen atmosphere, performing heat treatment for 2 hours, and naturally cooling to obtain the porous hard carbon material for the negative electrode of the sodium ion battery, and marking as a sample No. 1.
Examples 2 to 8
Preparation of composite sample No. 2-8
Examples 2-8 were conducted as in example 1, except that the type of hard carbon precursor added (instead of sodium carboxymethyl cellulose in example 1), and the heat treatment conditions (pretreatment temperature, high heat treatment temperature) were changed. And the samples obtained in the corresponding examples were numbered. See in particular table 1.
Table 1 porous hard carbon material samples prepared under different conditions
| Examples | Precursor species | Pretreatment temperature | High temperature heat treatment temperature |
| 2 # | Sodium carboxymethyl cellulose | 300℃ | 1300℃ |
| 3 # | Sodium carboxymethyl cellulose | 400℃ | 1400℃ |
| 4 # | Sodium carboxymethyl cellulose | 300℃ | 1500℃ |
| 5 # | Sodium carboxymethyl cellulose | 400℃ | 1500℃ |
| 6 # | Sodium alginate | 250℃ | 1300℃ |
| 7 # | Sodium carboxymethyl starch | 300℃ | 1200℃ |
| 8 # | Sodium polyacrylate | 400℃ | 1100℃ |
Example 9
X-ray diffraction analysis was performed on samples 1# to 8# respectively.
As is typical of sample # 1, fig. 1 is an XRD pattern of sample # 1, and as can be seen from fig. 1, peaks of (002) and (100) crystal planes of amorphous carbon appear at diffraction angles of about 23 ° and 44 °, respectively, while other impurity peaks are not observed, indicating that the obtained material is a hard carbon material.
The X-ray diffraction pattern of samples # 2 to # 8 is similar to that of sample # 1.
Example 10
And respectively carrying out field emission scanning electron microscope analysis on the 1# to 8# samples.
With the sample 1 as a representative, fig. 2 is a Field Emission Scanning Electron Microscope (FESEM) of the sample 1, and it can be seen that the hard carbon material is a random bulk material, the surface of the bulk is smooth, and the inside of the hard carbon bulk can be detected to be in a three-dimensional porous form from the cross section.
Fig. 3 is a further enlarged field emission scanning electron microscope image of sample # 1, which can show that the inside of the hard carbon material is rich in a large number of macropores, mesopores and micropore channels, and the three-dimensional channels are mutually crosslinked and communicated, so as to further prove the porous structure of the hard carbon material.
Example 11
Performance testing
Sample No. 1 powder prepared in example 1, a conductive agent (acetylene black) and a binder (CMC) were uniformly ground in a mass ratio of 8:1:1 (total 100 g), and then 1ml of deionized water was added to prepare a slurry, which was applied to an aluminum foil by a film coater, and then was kept at 100℃for 24 hours in a vacuum drying oven. And cutting the dried electrode slice into electrode slices with the diameter of 12mm by using a slicer, finally, taking metal sodium as a counter electrode in a glove box, and adopting a mixed solution of 1mol/L sodium perchlorate in ethylene carbonate, diethyl carbonate and dimethyl carbonate, wherein the volume ratio of the ethylene carbonate to the diethyl carbonate to the dimethyl carbonate is 1:1:1, and the membrane adopts Whatman GF/D to assemble the sodium ion button cell.
And performing performance test on the button cell.
FIG. 4 is a charge and discharge curve of sample # 1 for the first three cycles at a current density of 0.03A/g, where it is evident that the charge and discharge curve of porous hard carbon both contains significant plateau and ramp capacities. The first discharge capacity and the charge capacity were 472mAh/g and 310mAh/g, respectively.
The samples 2-8# prepared in examples 2-8 were prepared in the same manner to prepare sodium button cells, and the sodium button cells were subjected to 100 cycles of testing at a current density of 0.03A/g, and the results are shown in the following table, wherein the capacity units are mAh/g.
Table 2 test results of porous hard carbon material samples
Experimental results show that the composite material prepared in the examples 1-8 has higher capacity and first coulombic efficiency as the negative electrode material of the sodium ion battery, the graphitization degree of the porous hard carbon material can be increased along with the increase of the high-temperature carbonization temperature, and more active sites are provided for sodium ion intercalation and deintercalation, so that the capacity can be improved. However, the increase in temperature also results in a decrease in the spacing between graphite layers, and a decrease in the surface defects and functional group content, resulting in a decrease in capacity. Therefore, the sodium storage performance of the porous hard carbon material can be improved through optimization of the carbonization process.
Examples 12 to 14
Preparation of porous hard carbon material 12# -14# sample
Other preparation conditions were the same as in example 1 except that the heating rates in step (1) were changed to 1, 3 and 5℃per minute, respectively. The sodium ion battery performance of the porous hard carbon materials produced in examples 12-14 is given in Table 3.
Table 3 sodium ion battery performance of porous hard carbon materials of examples 12-14
The effect of different heating rates in step (1) on the sodium storage performance of the hard carbon produced was mainly compared in examples 12-14. In the heating pretreatment process of the hard carbon precursor material, the speed of forming sodium carbonate in the natural high molecular compound and the aggregation and combination condition are caused by the heating speed, so that the influence of the dispersity and the pore size of the porous structure in the final hard carbon material is caused, and the sodium storage performance of the porous hard carbon material is further influenced. Therefore, the heating rate in the step (1) is preferably 1-2 ℃/min.
The foregoing description is only a few examples of the present application and is not intended to limit the present application in any way, and although the present application is disclosed in the preferred examples, it is not intended to limit the present application, and any person skilled in the art may make some changes or modifications to the disclosed technology without departing from the scope of the technical solution of the present application, and the technical solution is equivalent to the equivalent embodiments.
Claims (8)
1. The preparation method of the porous hard carbon material for the negative electrode of the sodium ion battery is characterized by comprising the following steps of:
(1) Pretreating a hard carbon precursor in an inert atmosphere; the pretreatment is to heat up to 200-600 ℃ at a heating rate of 1-5 ℃/min, and to treat 1-6h at constant temperature under inert atmosphere;
the hard carbon precursor is at least one of sodium carboxymethyl cellulose, sodium carboxymethyl starch, sodium alginate and sodium polyacrylate;
(2) After natural cooling, ultrasonically washing the pretreated powder with deionized water, filtering and drying to obtain sodium carbonate-removed powder;
(3) Carbonizing the sodium carbonate-removed powder at high temperature in an inert atmosphere to obtain a porous hard carbon material for the negative electrode of the sodium ion battery;
the interlayer spacing of the porous hard carbon material is 0.36-0.39 nm; the porous structure of the porous hard carbon material comprises micropores, mesopores and macropores, wherein the pore diameter of the micropores is less than or equal to 2nm, the pore diameter of the mesopores is 2-50 nm, and the pore diameter of the macropores is more than or equal to 50nm.
2. The method for preparing a porous hard carbon material for a negative electrode of a sodium ion battery according to claim 1, wherein in the step (1), the inert atmosphere is one or both of nitrogen and argon.
3. The method for preparing a porous hard carbon material for a negative electrode of a sodium ion battery according to claim 1, wherein in the step (2), the mass ratio of the powder to deionized water is 1: (5-50); the ultrasonic washing time is 1-12 h.
4. The method for preparing a porous hard carbon material for a negative electrode of a sodium ion battery according to claim 1, wherein in the step (2), the drying mode is vacuum drying, the temperature is 60-120 ℃, and the drying time is 4-16h.
5. The method for preparing a porous hard carbon material for a negative electrode of a sodium ion battery according to claim 1, wherein the high-temperature carbonization in the step (3) is performed at a rate of 1-10 ℃/min to raise the temperature to 900-1500 ℃ and stay for 0.5-8 h.
6. A porous hard carbon material for a negative electrode of a sodium ion battery, which is characterized in that the porous hard carbon material is obtained by adopting the preparation method of any one of claims 1-5, and the interlayer spacing of the porous hard carbon material is 0.36-0.39 nm; the porous structure of the porous hard carbon material comprises micropores, mesopores and macropores, wherein the pore diameter of the micropores is less than or equal to 2nm, the pore diameter of the mesopores is 2-50 nm, and the pore diameter of the macropores is more than or equal to 50nm.
7. A negative electrode sheet comprising the porous hard carbon material according to claim 6.
8. A sodium ion half cell or sodium ion battery comprising the negative electrode sheet of claim 7.
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| CN115650202A (en) * | 2022-10-18 | 2023-01-31 | 仲恺农业工程学院 | Durian shell-based hard carbon negative electrode material and preparation method thereof |
| CN115744874A (en) * | 2022-12-29 | 2023-03-07 | 北京化工大学 | Hard carbon material and preparation method and application thereof |
| CN116040605A (en) * | 2022-12-22 | 2023-05-02 | 广东容钠新能源科技有限公司 | High-performance hard carbon negative electrode material for high-temperature sodium ion battery and preparation method thereof |
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| CN107732240A (en) * | 2017-09-05 | 2018-02-23 | 合肥工业大学 | The preparation method of anode material of lithium-ion battery, and negative material prepared therefrom |
| CN113735095A (en) * | 2021-08-06 | 2021-12-03 | 深圳市德方纳米科技股份有限公司 | Porous hard carbon material and preparation method and application thereof |
| CN115650202A (en) * | 2022-10-18 | 2023-01-31 | 仲恺农业工程学院 | Durian shell-based hard carbon negative electrode material and preparation method thereof |
| CN116040605A (en) * | 2022-12-22 | 2023-05-02 | 广东容钠新能源科技有限公司 | High-performance hard carbon negative electrode material for high-temperature sodium ion battery and preparation method thereof |
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