CN115020643A - Biomass-based hard carbon, preparation method thereof and application thereof in sodium-ion battery - Google Patents
Biomass-based hard carbon, preparation method thereof and application thereof in sodium-ion battery Download PDFInfo
- Publication number
- CN115020643A CN115020643A CN202210603931.5A CN202210603931A CN115020643A CN 115020643 A CN115020643 A CN 115020643A CN 202210603931 A CN202210603931 A CN 202210603931A CN 115020643 A CN115020643 A CN 115020643A
- Authority
- CN
- China
- Prior art keywords
- biomass
- hard carbon
- carbon
- ion battery
- based hard
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000002028 Biomass Substances 0.000 title claims abstract description 64
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 52
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 229910021385 hard carbon Inorganic materials 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 77
- 238000000498 ball milling Methods 0.000 claims abstract description 40
- 239000000463 material Substances 0.000 claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 21
- 235000017166 Bambusa arundinacea Nutrition 0.000 claims abstract description 17
- 235000017491 Bambusa tulda Nutrition 0.000 claims abstract description 17
- 241001330002 Bambuseae Species 0.000 claims abstract description 17
- 235000015334 Phyllostachys viridis Nutrition 0.000 claims abstract description 17
- 239000011425 bamboo Substances 0.000 claims abstract description 17
- 239000007773 negative electrode material Substances 0.000 claims abstract description 14
- 239000012298 atmosphere Substances 0.000 claims abstract description 9
- 241000609240 Ambelania acida Species 0.000 claims abstract description 8
- 239000010905 bagasse Substances 0.000 claims abstract description 8
- 230000008961 swelling Effects 0.000 claims abstract description 7
- 238000003801 milling Methods 0.000 claims abstract description 6
- 241000209140 Triticum Species 0.000 claims abstract description 5
- 235000021307 Triticum Nutrition 0.000 claims abstract description 5
- 239000010902 straw Substances 0.000 claims abstract description 5
- 239000002023 wood Substances 0.000 claims abstract description 5
- 239000000843 powder Substances 0.000 claims description 60
- 239000011148 porous material Substances 0.000 claims description 43
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 23
- 239000002245 particle Substances 0.000 claims description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 239000002243 precursor Substances 0.000 claims description 12
- 238000005245 sintering Methods 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 11
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- 238000000465 moulding Methods 0.000 claims description 9
- 238000003825 pressing Methods 0.000 claims description 9
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 238000001237 Raman spectrum Methods 0.000 claims description 5
- 238000002441 X-ray diffraction Methods 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 4
- 238000011049 filling Methods 0.000 claims description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 4
- 239000011780 sodium chloride Substances 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- LFTLOKWAGJYHHR-UHFFFAOYSA-N N-methylmorpholine N-oxide Chemical compound CN1(=O)CCOCC1 LFTLOKWAGJYHHR-UHFFFAOYSA-N 0.000 claims description 3
- 238000010000 carbonizing Methods 0.000 claims description 3
- IQQRAVYLUAZUGX-UHFFFAOYSA-N 1-butyl-3-methylimidazolium Chemical compound CCCCN1C=C[N+](C)=C1 IQQRAVYLUAZUGX-UHFFFAOYSA-N 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000011230 binding agent Substances 0.000 claims description 2
- 239000006258 conductive agent Substances 0.000 claims description 2
- 230000005284 excitation Effects 0.000 claims description 2
- 229910001220 stainless steel Inorganic materials 0.000 claims description 2
- 239000010935 stainless steel Substances 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 35
- 239000010406 cathode material Substances 0.000 abstract description 14
- 230000008569 process Effects 0.000 abstract description 7
- 238000010923 batch production Methods 0.000 abstract description 2
- 239000003792 electrolyte Substances 0.000 description 27
- 239000010410 layer Substances 0.000 description 16
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 15
- 229910001416 lithium ion Inorganic materials 0.000 description 15
- 239000000203 mixture Substances 0.000 description 15
- 238000001816 cooling Methods 0.000 description 13
- 238000010438 heat treatment Methods 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- 230000014759 maintenance of location Effects 0.000 description 12
- 238000012360 testing method Methods 0.000 description 12
- 239000011734 sodium Substances 0.000 description 11
- 229910019398 NaPF6 Inorganic materials 0.000 description 10
- 238000001069 Raman spectroscopy Methods 0.000 description 10
- 238000001179 sorption measurement Methods 0.000 description 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 8
- 239000012300 argon atmosphere Substances 0.000 description 8
- 239000010949 copper Substances 0.000 description 8
- 229910052744 lithium Inorganic materials 0.000 description 8
- 238000010298 pulverizing process Methods 0.000 description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 7
- 239000011149 active material Substances 0.000 description 7
- 238000000840 electrochemical analysis Methods 0.000 description 7
- 229910002804 graphite Inorganic materials 0.000 description 7
- 239000010439 graphite Substances 0.000 description 7
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 6
- 239000011324 bead Substances 0.000 description 6
- 238000003763 carbonization Methods 0.000 description 6
- 238000003860 storage Methods 0.000 description 6
- 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 5
- 238000005336 cracking Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000011888 foil Substances 0.000 description 4
- 230000002687 intercalation Effects 0.000 description 4
- 238000009830 intercalation Methods 0.000 description 4
- 239000002033 PVDF binder Substances 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 239000004570 mortar (masonry) Substances 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 230000002441 reversible effect Effects 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- 229910001290 LiPF6 Inorganic materials 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000005087 graphitization Methods 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 239000002194 amorphous carbon material Substances 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910003472 fullerene Inorganic materials 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 229910052752 metalloid Inorganic materials 0.000 description 1
- 150000002738 metalloids Chemical class 0.000 description 1
- 239000013081 microcrystal Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000009828 non-uniform distribution Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 239000002296 pyrolytic carbon Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
Images
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
- H01M4/36—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
-
- 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
- H01M4/13—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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Carbon And Carbon Compounds (AREA)
- Secondary Cells (AREA)
Abstract
The invention discloses biomass-based hard carbon, a preparation method thereof and application thereof in a sodium-ion battery. The method comprises the following steps: the biomass is subjected to mechanical ball milling, vibration milling or swelling pretreatment, and then the pretreated biomass material is carbonized and cracked under inert atmosphere to obtain the biomass-derived hard carbon with high closed porosity. The invention also provides application of the biomass hard carbon with high closed porosity prepared by the method as a sodium ion battery negative electrode material. The invention takes the biomasses such as bamboo, bagasse, wheat straw, wood and derivatives thereof as raw materials, has simple process and green and environment-friendly raw materials, is suitable for batch production, and the prepared hard carbon material has excellent electrochemical performance and can be used as an ideal cathode material of a sodium ion battery.
Description
Technical Field
The invention belongs to the technical field of high-energy cathode materials of biological carbon type sodium ion batteries, and particularly relates to biomass hard carbon with high closed porosity, a preparation method and application thereof.
Background
Lithium ion batteries have been widely used in energy storage systems due to their advantages of high power density and long cycle life, and have taken a leading position in the fields of electric vehicles and portable electronic products. But the application of lithium ion batteries in large-scale power storage is limited due to the non-uniform distribution and scarcity of lithium resources. The metal sodium and the metal lithium have similar physical and chemical properties, the sodium resource is widely distributed and the price is low, and the advantages make the sodium-ion battery very suitable for large-scale energy storage. The electrode material of the sodium ion battery is a key part of the battery and determines the specific energy, the service life and the like of the sodium ion battery. Many positive electrode materials for sodium ion batteries have been developed, but there are still many challenges to develop a negative electrode material suitable for practical application of sodium ion batteries. Therefore, research into high-performance electrode materials is important for the development of various sodium ion batteries.
The anode material that has been commercialized at present is mainly a carbon material, and generally, the carbon material may be classified into graphitized carbon, amorphous carbon, a novel carbon material, and the like according to the degree of graphitization and the difference of a microcrystalline structure. The graphitized carbon material has high graphitization degree, high specific capacity and a charge-discharge platform, but is sensitive to the composition of an electrolyte, poor in overcharge resistance and easy to damage graphite crystals in the charge-discharge process. The amorphous carbon material mainly comprises graphite microcrystals and an amorphous region, has high reversible lithium storage capacity, but lithium ions are difficult to be extracted after being inserted into micropores, so that poor cycle performance and high first irreversible capacity are caused. The novel carbon material mainly comprises fullerene, carbon nano tube, graphene and the like, and has high lithium storage capacity, but the preparation process is complex. At present, the sharp increase of the use amount of petroleum and coal causes serious environmental pollution problems, and the gradual depletion of reserves thereof also deepens people's understanding and worry about energy crisis. The development of new energy materials and energy storage devices with low cost, renewable and environmental friendliness has become a hot spot of current research. Therefore, the search for low-cost and excellent-performance carbon materials has become an important research direction in the field.
As a negative electrode material, graphite has been widely used in lithium ion batteries. During charging, lithium ions can be easily inserted into the graphite layer to form LiC 6 A structural compound. However, since the sodium ion size is much larger than the lithium ion, reversible high proportion of sodium intercalation compounds (with a chemical formula approximating NaC after intercalation) are not easily formed 70 ) Its specific capacity is very low. In contrast, various non-graphite structured carbon materials exhibit good reversible deintercalation of sodium ions. The hard carbon material is one of the most common carbon materials, has a macroscopic non-graphite structure, and contains graphite interlayers in a microscopic structure, and is considered to be the most practical negative electrode material of the sodium-ion battery at present.
The biomass wastes (such as bamboo, bagasse, wheat straw, wood and derivatives thereof and the like) have the characteristics of wide sources, sustainable regeneration, low pollution and low price, and the carbon material prepared by using the biomass wastes as the raw material can save the cost and relieve the problem of environmental pollution caused by a large amount of incineration wastes. Secondly, the biomass material often forms special texture structure and texture characteristics in the growth process, the microstructure of the biomass material can be still kept after carbonization, trace impurity elements such as potassium, silicon and the like can activate a carbon skeleton in the heat treatment process so as to enrich the pore structure of the material, and the biomass material is beneficial to improving the electrochemical performance of the electrode material in the charging and discharging processes of a sodium ion battery.
In the sodium ion battery, sodium ions are difficult to form stable intercalation compounds among graphite-like microcrystalline layers, and metalloid sodium deposited in closed pores at a low potential has stronger thermodynamic stability, so that the capacity of the carbon material can be remarkably improved by introducing a closed pore structure. In a lithium ion battery, lithium ions have a small radius, and thus can stably form an intercalation compound in a graphite-like layer, and have a considerable capacity. The hard carbon material does not require a large amount of closed pores in the lithium ion battery to increase capacity.
Disclosure of Invention
In view of the deficiencies of the prior art, the primary object of the present invention is to provide a biomass-based hard carbon. The material is characterized in that the material is a high-closed-pore-rate carbon material, can be used as a negative electrode material to be applied to a sodium ion secondary battery, and has a discharge capacity of 100-500 mAh.g -1 In the meantime.
Biomass-based hard carbon with closed pore volume of 0.04-0.5cm 3 ·g -1 。
The biomass-based hard carbon has a true density value of 0.8-2.1 g-cm -3 。
Closed pores are pore structures surrounded by the curved stacked carbon layers, and the closed pore volume is the closed pore volume. The amount of closed cells and the true density are related by the following equation:
in order to obtain the information of the amount of the closed pores, helium (medium with the smallest diameter) is introduced as a probe, and the volume of the closed pores is deduced reversely by detecting the true density of the material (combined with the density calculation of the non-porous graphite).
The biomass-based hard carbon has the particle size of 2-50um, the d002 value between carbon layers of 0.35-0.40nm, the aperture of 0.5-5nm and the specific surface area of 0.5-100m 2 ·g -1 。
The biomass-based hard carbon is prepared by using biomass as a precursor raw material, pretreating the raw material to change the crystal structure of the raw material, amorphizing the raw material, and carbonizing and cracking the precursor material in an inert atmosphere.
A second object of the present invention is to provide a method for preparing biomass-based hard carbon. The method uses rich, cheap and reproducible biomasses such as bamboo/bagasse/wheat straw/wood and derivatives thereof as precursors, and controls X-ray diffraction B/A value (amorphous value) and crystallinity (CrI ═ I ═ A 002 -I am )/I 002 ) And Raman spectrum value, a high-closed-pore-rate carbon material with high capacity and excellent rate performance is obtained after high-temperature sintering, and the preparation method is a hard carbon preparation method which has the advantages of low cost, simple preparation process, adjustable disorder degree, high carbon yield and suitability for large-scale production.
A method for preparing biomass-based hard carbon, comprising the steps of:
1) crushing biomass to obtain biomass coarse powder;
2) pretreating the biomass coarse powder to obtain a carbon material precursor; the carbon material precursor has an X-ray diffraction B/A value of 1.1 to 3.0 and a crystallinity CrI (CrI ═ I) 002 -I am )/I 002 ) 25% -70%; the ID/IG value of the Raman spectrum is 0.5-2;
3) carbonizing the carbon material precursor obtained in the step 2) in an inert atmosphere to obtain the carbon material.
The preparation method, step 1) the biomass comprises: one or more of bamboo, bagasse, wheat straw, wood and derivatives thereof.
The preparation method, the pretreatment method in the step 2) comprises one or more of mechanical ball milling, vibration milling and swelling.
The preparation method comprises the steps that the time of the mechanical ball milling pretreatment is 6-48h (preferably 12-24h), the rotation speed is 100-: (0.05-20) (preferably 1: 5-10), the ball milling medium and the pot body are made of one of agate, zirconia and stainless steel.
The preparation method comprises the steps that the vibration mill pretreatment time is 1-10h (preferably 4-6h), the filling rate is 30-60% (preferably 40-50%), the excitation force is 6000-16000N (preferably 12000-16000N), the ball-material ratio is 1: (0.1-10) (preferably 1: 5-10).
The preparation method has the swelling pretreatment time of 0.5-24h (preferably 6-12h), the pretreatment temperature of 30-290 ℃ (preferably 80-160 ℃), and solutes comprising N-methylmorpholine-N-oxide, NaOH, KOH, LiOH, LiCl, NaCl, [ BMIM ]]Cl、HCl、H 2 SO 4 One or more (preferably NaOH and NaCl), water, DMAc solution and alcohol solution (preferably water), wherein the solvent and solute are prepared at 0.1-10mol/L (preferably 1-5 mol/L).
In the preparation method, the temperature is raised to 900-1700 ℃ at the speed of 1-10 ℃/min (preferably 2 ℃/min) in the step 3), and then the temperature is kept for 1-5 hours (preferably 3 hours) after the temperature is raised to 1300-1500 ℃.
Further preferably: placing the carbon material precursor obtained in the step 2) in a mould at a temperature of 20-100 mm.min -1 The pressure is maintained for 5-20s, the forming pressure is 40-150MPa, and the obtained block material is placed in an inert atmosphere high-temperature sintering furnace.
The raw materials are carbonized and cracked through high-temperature sintering; and cooling to room temperature to obtain the high-closed-pore-rate carbon material with regular shape and soft structure.
The third purpose of the invention is to provide the application of the biomass-based hard carbon as the negative electrode material of the sodium-ion battery.
The fourth purpose of the invention is to provide a negative pole piece of a sodium ion battery, which comprises: the composite material comprises a current collector, a binder coated on the current collector, a conductive agent and the biomass-based hard carbon.
The fifth purpose of the invention is to provide a sodium ion secondary battery, which comprises the negative pole piece of the sodium ion battery.
The invention has the following beneficial effects:
(1) the invention firstly discovers that the X-ray diffraction B/A value (amorphous value) and the crystallinity (CrI ═ I) are controlled by the pretreatment condition 002 -I am )/I 002 ) And the Raman spectrum value can obtain the biological carbon material with high closed porosity, and provides a new technical breakthrough point for the technical field of preparation of the cathode material of the sodium-ion battery.
(2) Compared with the prior art, the method for preparing the biomass-based hard carbon with the high closed porosity uses biomass as a raw material, and obtains the biomass hard carbon material with the high closed porosity through pretreatment and high-temperature carbonization. The method has the advantages of simple process, green and environment-friendly used raw materials, suitability for batch production, strong repeatability and low cost, and the prepared biomass-based hard carbon with high closed porosity gives consideration to high capacity and excellent conductivity, and is a composite carbon material which has the advantages of low cost, simple preparation process, adjustable disorder degree, high carbon yield and suitability for large-scale production.
(3) The invention provides biomass-based high-closed-pore-rate hard carbon which can be used as a cathode material of a sodium ion secondary battery, has the advantages of high capacity, excellent rate capability, high working voltage, large energy density, stable cycle performance, excellent safety performance and the like, and only needs pretreatment such as mechanical ball milling, vibration milling, swelling and the like on raw materials, so that the capacity and rate capability of the sodium ion battery are effectively improved.
Drawings
FIG. 1 is an X-ray diffraction (XRD) pattern of bamboo powder (pellet to feed ratio of 1:10) at different pretreatment times.
FIG. 2 is a B/A (amorphous value) value curve of bamboo powder (ball to material ratio of 1:10) for different pretreatment times.
FIG. 3 is the Raman spectrum of bamboo powder (pellet to pellet ratio 1:10) at different pretreatment times.
FIG. 4 is I of bamboo powder (ball to feed ratio of 1:10) at different pretreatment times D /I G Curve line.
FIG. 5a is a Transmission Electron Microscope (TEM) image of carbon material powder particles prepared in comparative example 1.
FIG. 5b is a Transmission Electron Microscope (TEM) image of the carbon material powder particles prepared in example 1. (the curved stacked carbon layers enclose a closed pore structure, i.e. closed pores)
FIG. 6 is a graph showing that the carbon material prepared in comparative example 1 has a current density of 50mA g at 30 ℃ in a sodium-ion half-cell -1 First charge and discharge curves below.
FIG. 7 shows that the carbon material prepared in comparative example 3 has a current density of 50mA g at 30 ℃ in a lithium ion half cell -1 First charge and discharge curves below.
FIG. 8 is a Scanning Electron Microscope (SEM) image of carbon material powder particles prepared in example 1.
FIG. 9 shows that the carbon material prepared in example 1 has a current density of 50mA g at 30 ℃ in a sodium ion half-cell -1 First charge-discharge curve below.
FIG. 10 is a Scanning Electron Microscope (SEM) image of carbon material powder particles prepared in example 3.
FIG. 11 shows that the carbon material prepared in example 3 has a current density of 50mA g at 30 ℃ in a sodium ion half-cell -1 First charge-discharge curve below.
FIG. 12 shows that the carbon materials prepared in comparative example 1 and example 4 have a current density of 50mA g at 30 ℃ in a Na-ion half-cell -1 First charge and discharge curves below.
FIG. 13 is a graph showing the rate profile of the carbon material prepared in example 4 at 30 ℃ in a sodium ion half cell.
FIG. 14 shows 1000mA · g of the carbon material prepared in example 4 at 30 ℃ for a Na ion half cell -1 Large current cycling profile of (a).
Detailed Description
The invention is further illustrated, but not limited, by the following figures.
Comparative example 1
The embodiment of the invention provides a preparation method of a biomass-based sodium ion battery hard carbon negative electrode material, which comprises the following steps:
step (1): the biomass is prepared from bamboo by pulverizing to obtain coarse powder (1-3 mm).
Step (2): crushing and sieving the coarse powder to obtain a fine powder raw material with B/A being 1.05, CrI being 75.4% and ID/IG being 0.44 (shown in figures 1-4);
and (3): adding the fine powder raw material into a cylindrical mold with the inner diameter of 50mm, pressing and molding to obtain a block material, putting the block material into an argon atmosphere high-temperature sintering furnace, heating to 900 ℃, heating the raw material at high temperature in an argon atmosphere, and keeping the temperature for 3 hours to ensure that the raw material is subjected to carbonization and cracking reaction.
Specifically, in the press molding, the pressing speed is 60 mm/min -1 The dwell time is 8s, and the forming pressure is 70 MPa.
Specifically, the heating rate is 2 ℃/min.
And (4): and cooling to room temperature to obtain a blocky carbon material with regular shape and soft structure, namely the sodium ion battery cathode material.
Specifically, the cooling may be natural cooling, and the material is taken out of the high-temperature sintering furnace after being cooled to room temperature. The morphology of the prepared carbon material powder particles is shown in FIG. 5 a.
And (5): measuring the true density, the closed pore amount and the size of a small amount of the carbon material prepared above to obtain the true density of the carbon material of 2.21 g-cm -3 Closed pore volume of 0.010cm 3 ·g -1 The particle size is about 55 um. By Raman and N 2 The carbon layer spacing, pore diameter and specific surface area were 0.37nm, 0.47nm and 11.6m, respectively, as measured by adsorption isotherm 2 ·g -1 。
And (6): the carbon material prepared in the above way is used as an active material of a battery negative electrode material for preparing a sodium ion battery.
160mg of prepared carbon material powder, 20mg of conductive carbon black and 20mg of PVDF are weighed respectively according to the mass ratio of 8:1:1 and are uniformly stirred in an agate mortar, a proper amount of N-methylpyrrolidone (NMP) is dripped in, the mixture is stirred for 8 hours until the mixture is uniformly homogenized, the mixture is uniformly coated on the surface of copper (Cu) foil by using a scraper with the particle size of 100 micrometers, the copper (Cu) foil is dried for 12 hours at the temperature of 80 ℃ under the vacuum condition, the Cu foil with the active material is cut into a disk-shaped negative pole piece, and the disk-shaped negative pole piece is immediately transferred to a glove box for standby.
The assembly of the simulated cells was performed in a MIKROUNA glove box filled with Ar atmosphere using the prepared carbon material pole piece as the negative electrode, commercial electrolyte 1.0mol/L NaPF6/DME (1:1) (V: V) as the electrolyte, Na metal piece as the counter electrode, assembling 2016 coin cells.
And (3) placing the assembled button cell for 6 hours, placing the button cell in a 30 ℃ constant temperature test system, and carrying out charge and discharge tests on the button cell in a voltage interval of 0.01-2.0V (vs. Na +/Na, the same below). The results of the electrochemical tests are shown in Table 1 and FIG. 6, and it can be seen from the first charge-discharge curve of FIG. 6 that the half cell using 1.0mol/L NaPF6/DME as the electrolyte has a voltage of 50mA g -1 The first coulombic efficiency under the current density of (1) is low and is only 39.82%, and the specific discharge capacity of the hard carbon negative electrode in the electrolyte in the first circle is 294.52 mAh.g -1 The charging specific capacity of the first circle is 117.28mAh g -1 The specific discharge capacity of the second coil is 145.43mAh g -1 The specific discharge capacity after 50 cycles is 71.42mAh g -1 The capacity retention after 50 cycles was 49.11%.
Comparative example 2
The embodiment of the invention provides a preparation method of a hard carbon negative electrode material based on a biomass sodium ion battery, which comprises the following steps:
step (1): the biomass is prepared from bamboo by pulverizing to obtain coarse powder (1-3 mm).
Step (2): the coarse powder was ground by vibration milling for 0.5 hour to obtain a fine powder material having a B/A of 1.43, a CrI of 73.3% and an ID/IG of 0.67
Specifically, in the vibration mill, the steel balls and the fine powder raw materials are mixed according to the mass ratio of 1:5, the filling rate is 50%, the vibration mill time is 0.5h, and the exciting force is 12000N.
Steps (3 to 4) were the same as in comparative example 1.
And (5): measuring the true density, the closed pore amount and the size of a small amount of the carbon material prepared above to obtain the true density of the carbon material of 2.15 g-cm -3 Closed pore volume of 0.023cm 3 ·g -1 The particle size is about 40 um. The carbon-layer spacing was 0.37nm, pore size 0.47nm, ratio as measured by Raman and N2 adsorption isothermsSurface area 12.4m 2 ·g -1 。
And (6): the carbon material prepared in the above way is used as an active material of a battery negative electrode material for preparing a sodium ion battery. The specific operation steps are the same as the step (6) of the comparative example 1.
The electrochemical test results are shown in Table 1, and the carbon material is applied to a half cell with 1.0mol/L NaPF6/DME as electrolyte at 50 mA.g -1 The first coulombic efficiency under the current density is low and is only 48.63 percent, and the first-circle discharge specific capacity of the hard carbon cathode in the electrolyte is 272.34 mAh.g -1 The charging specific capacity of the first circle is 132.44 mAh g -1 The specific discharge capacity of the second ring is 141.93mAh g -1 The specific discharge capacity after 50 cycles is 71.42mAh g -1 And the capacity retention rate after 50 cycles is 50.32%.
Comparative example 3
Step (1): the biomass is prepared from bamboo by pulverizing to obtain coarse powder (1-3 mm).
Step (2): the coarse powder was subjected to mechanical ball milling for 6 hours to obtain a fine powder material having B/a of 1.68, CrI of 40.9 and ID/IG of 0.83.
Specifically, in mechanical ball milling, ball milling beads and fine powder raw materials are mixed according to the mass ratio of 1:10, the mechanical ball milling time is 6 hours, the ball milling rotating speed is 350r/min, and a ball milling medium and a tank body are made of agate.
And (3): adding the fine powder raw material into a cylindrical mold with the inner diameter of 50mm, pressing and molding to obtain a block material, putting the block material into an argon atmosphere high-temperature sintering furnace, heating to 900 ℃, heating the raw material at high temperature in an argon atmosphere, and keeping the temperature for 3 hours to ensure that the raw material is subjected to carbonization and cracking reaction.
Specifically, in the press molding, the pressing speed is 60 mm/min -1 The dwell time is 8s, and the forming pressure is 70 MPa.
Specifically, the heating rate is 2 ℃/min.
And (4): and cooling to room temperature to obtain a blocky carbon material with regular shape and soft structure, namely the lithium ion battery cathode material.
Specifically, the cooling may be natural cooling, and the material is taken out of the high-temperature sintering furnace after being cooled to room temperature.
And (5): measuring the true density, the closed pore amount and the size of a small amount of the carbon material prepared above to obtain the true density of the carbon material of 2.03 g-cm -3 Closed cell content of 0.050cm 3 ·g -1 The particle size is about 12 um. The carbon-layer spacing is 0.38nm, the pore diameter is 1.3nm, and the specific surface area is 22.9m measured by Raman and N2 adsorption isotherms 2 ·g -1 。
And (6): the carbon material prepared in the above way is used as an active material of a battery negative electrode material for preparing a lithium ion battery.
160mg of prepared carbon material powder, 20mg of conductive carbon black and 20mg of PVDF are weighed according to the mass ratio of 8:1:1 respectively and stirred uniformly in an agate mortar, a proper amount of N-methylpyrrolidone (NMP) is dripped into the mixture, the mixture is stirred for 8 hours until the mixture is homogenized, the mixture is uniformly coated on the surface of copper (Cu) foil by a scraper of 100 mu m, the mixture is dried for 12 hours at 80 ℃ under a vacuum condition, the Cu foil with the active material is cut into a disk-shaped negative pole piece, and then the disk-shaped negative pole piece is transferred to a glove box for later use.
The assembly of the simulated cells was carried out in a MIKROUNA glove box filled with Ar atmosphere using the prepared carbon material pole piece as the negative electrode, commercial electrolyte 1.0mol/L LiPF6/EC: DMC: EMC: 1:1:1 as the electrolyte and Li metal piece as the counter electrode to assemble 2016 coin cells.
And (3) placing the assembled button cell in a 30 ℃ constant temperature test system after the button cell is placed for 6 hours, and carrying out charge and discharge tests on the button cell in a voltage range of 0.01-2.0V (vs. Li +/Li). The electrochemical test results are shown in Table 1 and FIG. 7, and it can be seen from FIG. 7 that the lithium ion half cell assembled in comparative example 3 was operated at 50mA · g -1 The first coulombic efficiency under the current density is 72.91 percent, and the first-circle discharge specific capacity of the hard carbon negative electrode in the lithium electrolyte is 218.97 mAh.g -1 The charging specific capacity of the first circle is 159.67mAh g -1 The specific discharge capacity of the second coil is 165.79mAh g -1 And the specific discharge capacity after 50 cycles is 94.05mAh g -1 And the capacity retention rate after 50 cycles is 56.73%.
From this comparative example, it can be found that the sodium storage performance is different from the lithium storage performance, indicating that the closed pore structure in the pyrolytic carbon functions differently in the lithium ion battery and the sodium ion battery, and the lithium storage performance in the lithium battery is poor.
Example 1
The embodiment of the invention provides a preparation method of a biomass-based sodium-ion battery cathode material, which comprises the following steps:
step (1): the biomass is prepared from bamboo by pulverizing to obtain coarse powder (1-3 mm).
Step (2): the coarse powder was mechanically ball-milled for 6 hours and refined to obtain a fine powder material of B/a ═ 1.65, CrI ═ 41.2%, and ID/IG ═ 0.81 (see fig. 1 to 4).
Specifically, in mechanical ball milling, ball milling beads and fine powder raw materials are mixed according to the mass ratio of 1:5, the mechanical ball milling time is 6 hours, the ball milling rotating speed is 350r/min, and a ball milling medium and a tank body are made of agate.
And (3): adding the fine powder raw material into a cylindrical mold with the inner diameter of 50mm, pressing and molding to obtain a block material, putting the block material into an argon atmosphere high-temperature sintering furnace, heating to 900 ℃, heating the raw material at high temperature in an argon atmosphere, and keeping the temperature for 3 hours to ensure that the raw material is subjected to carbonization and cracking reaction.
Specifically, in the press molding, the pressing speed is 60 mm/min -1 The dwell time is 8s, and the forming pressure is 70 MPa.
Specifically, the heating rate is 2 ℃/min.
And (4): and cooling to room temperature to obtain a blocky carbon material with regular shape and soft structure, namely the sodium ion battery cathode material.
Specifically, the cooling may be natural cooling, and the material is taken out of the high-temperature sintering furnace after being cooled to room temperature. The morphology of the prepared carbon material powder particles is shown in fig. 5b and fig. 8.
And (5): measuring the true density, the closed pore amount and the size of a small amount of the carbon material prepared above to obtain the carbon material with the true density of 1.99 g-cm -3 Closed pore volume of 0.060cm 3 ·g -1 The particle size is about 12 um. The carbon layer spacing is 0.38nm, the pore diameter is 1.3nm, the specific surface area is measured by Raman and N2 adsorption isotherm22.9m 2 ·g -1 。
And (6): the carbon material prepared in the above way is used as an active material of a battery negative electrode material for preparing a sodium ion battery.
160mg of prepared carbon material powder, 20mg of conductive carbon black and 20mg of PVDF are weighed according to the mass ratio of 8:1:1 respectively and stirred uniformly in an agate mortar, a proper amount of N-methylpyrrolidone (NMP) is dripped into the mixture, the mixture is stirred for 8 hours until the mixture is homogenized, the mixture is uniformly coated on the surface of copper (Cu) foil by a scraper of 100 mu m, the mixture is dried for 12 hours at 80 ℃ under a vacuum condition, the Cu foil with the active material is cut into a disk-shaped negative pole piece, and then the disk-shaped negative pole piece is transferred to a glove box for later use.
The assembly of the simulated cells was performed in a MIKROUNA glove box filled with Ar atmosphere using the prepared carbon material pole piece as the negative electrode, commercial electrolyte 1.0mol/L NaPF6/DME as the electrolyte, Na metal piece as the counter electrode, to assemble 2016 coin cells.
And (3) placing the assembled button cell for 6 hours, placing the button cell in a 30 ℃ constant temperature test system, and carrying out charge and discharge tests on the button cell in a voltage interval of 0.01-2.0V (vs. Na +/Na, the same below). The results of the electrochemical tests are shown in Table 1 and FIG. 9, and it can be seen from the first charge-discharge curve of FIG. 9 that the half cell using 1.0mol/L NaPF6/DME as the electrolyte has a voltage of 50mA g -1 The first coulombic efficiency at the current density of (1) is 57.74%, and the first-turn specific discharge capacity is 348.33mAh g -1 The charging specific capacity of the first circle is 201.11mAh g -1 The discharge specific capacity of the second circle is 209.35mAh g -1 The specific discharge capacity after 50 cycles is 128.54mAh g -1 The capacity retention rate after 50 cycles was 61.40%.
Example 2
The embodiment of the invention provides a preparation method of a biomass-based sodium-ion battery cathode material, which comprises the following steps:
step (1): the biomass is prepared from bamboo by pulverizing to obtain coarse powder (1-3 mm).
Step (2): the coarse powder was mechanically ball-milled for 10 hours and refined to obtain a fine powder material of B/a ═ 1.74, CrI ═ 37.2%, and ID/IG ═ 0.92 (see fig. 1).
Specifically, in mechanical ball milling, ball milling beads and fine powder raw materials are mixed according to the mass ratio of 1:10, the mechanical ball milling time is 6 hours, the ball milling rotating speed is 350r/min, and a ball milling medium and a tank body are made of agate.
Steps (3 to 4) were the same as in example 1.
And (5): measuring the true density, the closed pore amount and the size of a small amount of the carbon material prepared above to obtain the carbon material with the true density of 1.86 g-cm -3 Closed pore volume 0.095cm 3 ·g -1 The particle size is about 10 um. The carbon-layer spacing, pore diameter and specific surface area of the material were 0.391nm, 1.5nm and 13.8m, as measured by Raman and N2 adsorption isotherms 2 ·g -1 。
Step (6) cell preparation and electrochemical testing were the same as in the examples.
The electrochemical test results are shown in Table 1, and the half cell using 1.0mol/L NaPF6/DME as electrolyte is at 50 mA.g -1 The first coulombic efficiency under the current density of the lithium ion battery is 68.27 percent, and the specific discharge capacity of the first ring is 421.78 mAh g -1 The charging specific capacity of the first circle is 287.95mAh g -1 The specific discharge capacity of the second coil is 273.12mAh g -1 The specific discharge capacity after 50 cycles is 200.58mAh g -1 The capacity retention after 50 cycles was 73.44%.
Example 3
The embodiment of the invention provides a preparation method of a biomass-based sodium-ion battery cathode material, which comprises the following steps:
step (1): the biomass is prepared from bamboo by pulverizing to obtain coarse powder with particle diameter of 1-3 mm.
Step (2): the coarse powder was subjected to mechanical ball milling for 6 hours and refined to obtain a fine powder raw material having a B/a of 1.68, a CrI of 40.9 and an ID/IG of 0.83
Specifically, in the mechanical ball milling, ball milling beads and fine powder raw materials are mixed according to a mass ratio of 1:10, the mechanical ball milling time is 6 hours, the ball milling rotating speed is 350r/min, and the ball milling medium and the tank body are agate.
Steps (3 to 4) were the same as in example 1. The SEM image of the prepared carbon material is fig. 10.
And (5): taking small amount of the above preparationThe obtained carbon material was measured for true density, closed pore amount and size, and the true density of the carbon material was 2.01 g/cm -3 Closed pore volume of 0.055cm 3 ·g -1 The particle size is about 14 um. The carbon-layer spacing was 0.39nm, the pore diameter was 2.2nm, and the specific surface area was 27.3m as measured by Raman and N2 adsorption isotherms 2 ·g -1 。
Step (6) cell preparation and electrochemical testing were the same as in the examples.
The electrochemical test results are shown in Table 1 and FIG. 11, and it can be seen from the first charge-discharge curve of FIG. 11 that the half-cell using 1.0mol/L LiPF6/EC, DMC, EMC 1:1:1 as electrolyte is at 50 mA.g -1 The first coulombic efficiency under the current density of (1) is lower and is only 42.47%, and the specific discharge capacity of the hard carbon negative electrode in the electrolyte in the first circle is 363.87mAh g -1 The charging specific capacity of the first circle is 154.53mAh g -1 The discharge specific capacity of the second ring is 156.06mAh g -1 And the specific discharge capacity after 50 cycles of circulation is 92.53mAh g -1 And the capacity retention rate after 50 cycles is 59.29%.
Example 4
The embodiment of the invention provides a preparation method of a biomass-based sodium-ion battery negative electrode material, which comprises the following steps:
step (1): the biomass is prepared from bamboo by pulverizing to obtain coarse powder with particle diameter of 1-3 mm.
Step (2): the coarse powder was mechanically ball-milled for 6 hours and refined to obtain a fine powder material having B/a of 1.68, CrI of 40.9% and ID/IG of 0.83.
Specifically, in the mechanical ball milling, ball milling beads and fine powder raw materials are mixed according to a mass ratio of 1:10, the mechanical ball milling time is 6 hours, the ball milling rotating speed is 350r/min, and the ball milling medium and the tank body are agate.
And (3): adding the fine powder raw material into a cylindrical mold with the inner diameter of 50mm, pressing and molding to obtain a block material, putting the block material into an argon atmosphere high-temperature sintering furnace, heating to 1500 ℃, carrying out high-temperature heating on the raw material in an argon atmosphere, and keeping the temperature for 3 hours to ensure that the raw material is subjected to carbonization and cracking reaction.
In particular, in press formingThe pressing speed is 60 mm/min -1 The dwell time is 8s, and the forming pressure is 70 MPa.
Specifically, the heating rate is 2 ℃/min.
And (4): and cooling to room temperature to obtain a blocky carbon material with regular shape and soft structure, namely the sodium ion battery cathode material.
Specifically, the cooling may be natural cooling, and the material is taken out of the high-temperature sintering furnace after being cooled to room temperature.
And (5): a small amount of the carbon material prepared above was subjected to true density, closed cell content and size measurement to obtain a carbon material having a true density of 1.77 g-cm -3 Closed pore volume 0.122cm 3 ·g -1 The particle size is about 5 um. The carbon-layer spacing was 0.39nm, the pore diameter was 3.5nm, and the specific surface area was 29.1m as measured by Raman and N2 adsorption isotherms 2 ·g -1 。
Step (6) cell preparation and electrochemical testing were the same as in the examples.
The results of the electrochemical tests are shown in Table 1 and FIGS. 12-14, and it can be seen from the first charge-discharge curve of FIG. 12 that the half-cell using 1.0mol/L NaPF6/DME as the electrolyte has a power of 50mA g -1 The first coulombic efficiency under the current density of (1) is 66.66%, and the specific discharge capacity of the hard carbon negative electrode in the electrolyte in the first circle is 493.61 mAh g -1 The charging specific capacity of the first circle is 329.06mAh g -1 The specific discharge capacity of the second ring is 341.87mAh g -1 The specific discharge capacity after 50 cycles is 266.73mAh g -1 The capacity retention after 50 cycles was 78.02%.
Example 5
The embodiment of the invention provides a preparation method of a biomass-based sodium-ion battery cathode material, which comprises the following steps:
step (1): the biomass is a mixture of bamboo and bagasse in a mass ratio of 1:1, pulverizing to obtain a coarse powder raw material with B/a of 1.37, CrI of 57.6 and ID/IG of 0.43.
Step (2): the coarse powder was mechanically ball-milled for 6 hours and refined to obtain a fine powder material having B/a of 1.65, CrI of 41.5 and ID/IG of 0.80.
Specifically, in the mechanical ball milling, ball milling beads and fine powder raw materials are mixed according to a mass ratio of 1:10, the mechanical ball milling time is 6 hours, the ball milling rotating speed is 350r/min, and the ball milling medium and the tank body are agate.
Steps (3 to 4) were the same as in example 1.
And (5): measuring the true density, the closed pore amount and the size of a small amount of the carbon material prepared above to obtain the true density of the carbon material of 2.04 g-cm -3 Closed pore volume 0.048cm 3 ·g -1 The particle size is about 12 um. The carbon-layer spacing is 0.38nm, the pore diameter is 1.4nm, and the specific surface area is 20.2m measured by Raman and N2 adsorption isotherms 2 ·g -1 。
Step (6) cell preparation and electrochemical testing were the same as in the examples.
As shown in Table 1, the half-cell using 1.0mol/L NaPF6/DME as electrolyte was operated at 50mA g -1 The first coulombic efficiency under the current density of the electrolyte is 66.16 percent, and the first-circle specific discharge capacity of the hard carbon cathode in the electrolyte is 232.65 mAh.g -1 The charging specific capacity of the first circle is 153.91mAh g -1 The specific discharge capacity of the second ring is 189.33 mAh g -1 The specific discharge capacity after 50 cycles is 114.20mAh g -1 And the capacity retention rate after 50 cycles is 60.32%.
Example 6
The embodiment of the invention provides a preparation method of a biomass-based sodium-ion battery cathode material, which comprises the following steps:
step (1): bagasse was selected as a biomass, and pulverized to obtain coarse powder having B/a of 1.21, CrI of 47.1, and ID/IG of 0.39.
Step (2): carrying out vibration milling on the coarse powder for 2 hours and refining the coarse powder to obtain a fine powder raw material with B/A being 1.62, CrI being 41.9% and ID/IG being 0.73;
specifically, in the vibration mill, the steel balls and the fine powder raw materials are mixed according to the mass ratio of 1:5, the filling rate is 50%, the vibration mill time is 2h, and the exciting force is 12000N.
The procedure (3-4) was the same as in example 1.
And (5): prepared from a small amount of the aboveThe carbon material (2) was subjected to measurement of true density, closed cell content and size, and found to have a true density of 1.99 g/cm -3 Closed pore volume of 0.060cm 3 ·g -1 The particle size is about 30 um. The carbon layer spacing, the pore diameter and the specific surface area of the material are respectively 0.375nm, 0.79nm and 16.4m measured by Raman and N2 adsorption isotherms 2 ·g -1 。
Step (6) cell preparation and electrochemical testing were the same as in the examples.
As shown in Table 1, the half cell using 1.0mol/L NaPF6/DME as the electrolyte was operated at 50mA · g -1 The first coulombic efficiency under the current density of the electrolyte is 49.69 percent, and the first-circle specific discharge capacity of the hard carbon cathode in the electrolyte is 355.26 mAh.g -1 The charging specific capacity of the first circle is 176.53mAh g -1 The specific discharge capacity of the second ring is 178.24 mAh g -1 The specific discharge capacity after 50 cycles is 108.76mAh g -1 The capacity retention after 50 cycles was 61.02%.
Example 7
The embodiment of the invention provides a preparation method of a biomass-based sodium-ion battery cathode material, which comprises the following steps:
step (1): the biomass is selected from bagasse, and is crushed to obtain coarse powder.
Step (2): swelling the coarse powder for 40min to obtain fine powder with B/A of 1.61, CrI of 41.8 and ID/IG of 0.73
Specifically, the solvent is 80% by mass of N-methylmorpholine-N-oxide aqueous solution, the treatment time is 40min, the treatment temperature is 80 ℃, and the solvent is dried after filtration.
Steps (3 to 4) were the same as in example 1.
And (5): measuring the true density, the closed pore amount and the size of a small amount of the carbon material prepared above to obtain the carbon material with the true density of 2.00 g-cm -3 Closed pore volume of 0.057cm 3 ·g -1 The particle size is about 30 um. The carbon-layer spacing, pore diameter and specific surface area of the material were 0.38nm, 1.1nm and 17.4m, as measured by Raman and N2 adsorption isotherms 2 ·g -1 。
Step (6) cell preparation and electrochemical testing were the same as in the examples.
As shown in Table 1, the half cell using 1.0mol/L NaPF6/DME as the electrolyte was operated at 50mA · g -1 The first coulombic efficiency under the current density of the electrolyte is 50.33 percent, and the first-circle specific discharge capacity of the hard carbon cathode in the electrolyte is 364.99 mAh.g -1 The charging specific capacity of the first circle is 183.70mAh g -1 The specific discharge capacity of the second coil is 190.58 mAh g -1 The specific discharge capacity after 50 cycles is 119.68mAh g -1 The capacity retention rate after 50 cycles was 62.80%.
The above description is only exemplary of the present invention and should not be taken as limiting, any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
TABLE 1 the following tables of relevant parameters for the assembled half-cells of comparative examples 1 to 3 and examples 1 to 7
Injecting: the capacity retention rate refers to the retention rate after 50 cycles, and the first cycle belongs to the formation process relative to the second cycle.
Claims (13)
1. A biomass-based hard carbon characterized by a closed pore volume of 0.04-0.5cm 3 ·g -1 。
2. The biomass-based hard carbon according to claim 1, wherein the true density value is 0.8-2.1 g-cm -3 。
3. The biomass-based hard carbon according to claim 1, wherein the hard carbon has a particle diameter of 2 to 50um, a carbon layer spacing d002 value of 0.35 to 0.40nm, a pore diameter of 0.5 to 5nm, and a specific surface area of 0.5 to 100m 2 ·g -1 。
4. A preparation method of biomass-based hard carbon is characterized by comprising the following steps:
1) crushing biomass to obtain biomass coarse powder, wherein the preferred particle size of a biomass precursor is 1-3 mm;
2) pretreating the biomass coarse powder to obtain a carbon material precursor; the carbon material precursor has an X-ray diffraction B/A value of 1.15 to 3.0, a crystallinity CrI of 25 to 70%, and CrI ═ I (I) 002 -I am )/I 002 (ii) a The ID/IG value of the Raman spectrum is 0.5-2;
3) carbonizing the carbon material precursor obtained in the step 2) in an inert atmosphere to obtain the carbon material.
5. The method of claim 4, wherein the biomass in step 1) comprises: one or more of bamboo, bagasse, wheat straw, wood and derivatives thereof.
6. The method of claim 4, wherein the pretreatment in step 2) comprises one or more of mechanical ball milling, vibration milling, and swelling.
7. The preparation method according to claim 4, wherein the time of the mechanical ball milling pretreatment is 6-48h, preferably 12-24h, the rotation speed is 100-: (0.05-20), preferably 1: (5-10), the ball milling medium and the tank body are one of agate, zirconia and stainless steel.
8. The preparation method according to claim 4, wherein the vibration mill pretreatment time is 1-10h, preferably 4-6h, the filling rate is 30-60%, preferably 40-50%, the excitation force is 6000-16000N, preferably 12000-16000N, the ball-to-material ratio is 1: (0.1-10), preferably 1: (5-10).
9. According to claimThe method of claim 4, wherein the swelling pretreatment time is 0.5 to 24 hours, preferably 6 to 12 hours, the pretreatment temperature is 30 to 290 ℃, preferably 80 to 160 ℃, and the solute comprises N-methylmorpholine-N-oxide, NaOH, KOH, LiOH, LiCl, NaCl, [ BMIM ]]Cl、HCl、H 2 SO 4 Preferably NaOH and NaCl, and the solvent is one or more of water, DMAc solution and alcohol solution, preferably water, and the solution is prepared by the above solvents and solutes at 0.1-10mol/L, preferably 1-5 mol/L.
10. The method according to claim 4, wherein the temperature in step 3) is raised to 900-1700 ℃ at a rate of 1-10 ℃/min, preferably 2 ℃/min, and then kept constant for 1-5 hours, preferably 3 hours, after the temperature is raised to 1300-1500 ℃; preferably, the carbon material precursor obtained in the step 2) is placed in a mould at a speed of 20-100 mm.min -1 Pressing and molding at the speed of (1), keeping the pressure for 5-20s, and placing the obtained block material in an inert atmosphere high-temperature sintering furnace at the molding pressure of 40-150 MPa.
11. Use of the biomass-based hard carbon according to any one of claims 1 to 3 or the biomass-based hard carbon produced by the method according to any one of claims 4 to 10 as a negative electrode material for sodium-ion batteries.
12. A negative electrode sheet for a sodium ion battery, comprising: a current collector, a binder coated on the current collector, a conductive agent and the biomass-based hard carbon according to any one of claims 1 to 3, or the biomass-based hard carbon prepared by the method according to any one of claims 4 to 10.
13. A sodium ion secondary battery comprising the negative electrode tab of the sodium ion battery of claim 12.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2021110554850 | 2021-09-09 | ||
| CN202111055485 | 2021-09-09 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115020643A true CN115020643A (en) | 2022-09-06 |
| CN115020643B CN115020643B (en) | 2024-08-06 |
Family
ID=83071864
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210603931.5A Active CN115020643B (en) | 2021-09-09 | 2022-05-31 | Hard carbon based on biomass, preparation method thereof and application thereof in sodium ion battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115020643B (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115744871A (en) * | 2022-11-26 | 2023-03-07 | 中南大学 | Bagasse-based sodium ion battery hard carbon negative electrode active material, and preparation and application thereof |
| CN115818634A (en) * | 2022-12-01 | 2023-03-21 | 山西沁新能源集团股份有限公司 | Method for preparing sodium-ion battery negative electrode material by taking cedar as raw material |
| CN116404128A (en) * | 2023-03-30 | 2023-07-07 | 湖北万润新能源科技股份有限公司 | Porous hard carbon anode material and preparation method and application thereof |
| CN117069093A (en) * | 2023-09-15 | 2023-11-17 | 福建省鑫森炭业股份有限公司 | Preparation method of hard carbon anode material |
| CN117466278A (en) * | 2023-11-01 | 2024-01-30 | 东北大学 | Method for ball milling modification of hard carbon material and application of ball milling modification of hard carbon material in negative electrode of sodium ion battery |
| CN117550587A (en) * | 2024-01-11 | 2024-02-13 | 邢台旭阳新能源科技有限公司 | Negative electrode material and preparation method and application thereof |
| CN117735527A (en) * | 2024-02-21 | 2024-03-22 | 山东埃尔派粉体科技股份有限公司 | Biomass hard carbon anode material, preparation method thereof and sodium ion battery based on biomass hard carbon anode material |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102386384A (en) * | 2011-11-28 | 2012-03-21 | 深圳市贝特瑞新能源材料股份有限公司 | Spherical hard carbon lithium ion battery cathode material and preparation method thereof |
| JP2014205596A (en) * | 2013-04-15 | 2014-10-30 | 健 増長 | Method for producing carbon material, carbon material, and secondary battery |
| CN105514507A (en) * | 2016-02-02 | 2016-04-20 | 陕西科技大学 | Preparation method of paper-derived micro- and nano-structure hard carbon materials |
| CN109004199A (en) * | 2018-08-01 | 2018-12-14 | 北京理工大学 | A kind of preparation method of sodium-ion battery cathode biomass hard carbon material |
| US20190097275A1 (en) * | 2017-09-26 | 2019-03-28 | David Mitlin | Selenium impregnated materials as free-standing electrodes |
| CN109921018A (en) * | 2017-12-13 | 2019-06-21 | 宁波杉杉新材料科技有限公司 | The preparation method of sodium-ion battery high capacity biomass hard charcoal negative electrode material |
| WO2020174496A1 (en) * | 2019-02-28 | 2020-09-03 | Kpit Technologies Limited | A high-power density sodium-ion battery |
| JP2021077635A (en) * | 2019-11-01 | 2021-05-20 | 学校法人東京理科大学 | Negative electrode active material, manufacturing method thereof, negative electrode, and sodium ion battery |
| CN113113602A (en) * | 2021-04-06 | 2021-07-13 | 常德速碳新能源科技有限公司 | Hard carbon negative electrode material for lithium ion secondary battery and preparation method thereof |
| CN113912039A (en) * | 2021-09-22 | 2022-01-11 | 中南大学 | Sulfur-doped biomass hard carbon material and preparation method and application thereof |
| CN114388736A (en) * | 2021-12-15 | 2022-04-22 | 海南大学 | Method for preparing lithium/sodium ion battery hard carbon cathode by using biomass charcoal |
-
2022
- 2022-05-31 CN CN202210603931.5A patent/CN115020643B/en active Active
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102386384A (en) * | 2011-11-28 | 2012-03-21 | 深圳市贝特瑞新能源材料股份有限公司 | Spherical hard carbon lithium ion battery cathode material and preparation method thereof |
| JP2014205596A (en) * | 2013-04-15 | 2014-10-30 | 健 増長 | Method for producing carbon material, carbon material, and secondary battery |
| CN105514507A (en) * | 2016-02-02 | 2016-04-20 | 陕西科技大学 | Preparation method of paper-derived micro- and nano-structure hard carbon materials |
| US20190097275A1 (en) * | 2017-09-26 | 2019-03-28 | David Mitlin | Selenium impregnated materials as free-standing electrodes |
| CN109921018A (en) * | 2017-12-13 | 2019-06-21 | 宁波杉杉新材料科技有限公司 | The preparation method of sodium-ion battery high capacity biomass hard charcoal negative electrode material |
| CN109004199A (en) * | 2018-08-01 | 2018-12-14 | 北京理工大学 | A kind of preparation method of sodium-ion battery cathode biomass hard carbon material |
| WO2020174496A1 (en) * | 2019-02-28 | 2020-09-03 | Kpit Technologies Limited | A high-power density sodium-ion battery |
| JP2021077635A (en) * | 2019-11-01 | 2021-05-20 | 学校法人東京理科大学 | Negative electrode active material, manufacturing method thereof, negative electrode, and sodium ion battery |
| CN113113602A (en) * | 2021-04-06 | 2021-07-13 | 常德速碳新能源科技有限公司 | Hard carbon negative electrode material for lithium ion secondary battery and preparation method thereof |
| CN113912039A (en) * | 2021-09-22 | 2022-01-11 | 中南大学 | Sulfur-doped biomass hard carbon material and preparation method and application thereof |
| CN114388736A (en) * | 2021-12-15 | 2022-04-22 | 海南大学 | Method for preparing lithium/sodium ion battery hard carbon cathode by using biomass charcoal |
Non-Patent Citations (4)
| Title |
|---|
| SIYU ZHOU ET AL.: "Regulating closed pore structure enables significantly improved sodium storage for hard carbon pyrolyzing at relatively low temperature", 《SUSMAT.》, vol. 02, no. 03, pages 357 - 367 * |
| WANG JIN ET AL.: "Green large-scale production of N/O-dual doping hard carbon derived from bagasse as high-performance anodes for sodium-ion batteries", 《JOURNAL OF CENTRAL SOUTH UNIVERSITY》, vol. 28, no. 02, pages 361 - 369, XP037374484, DOI: 10.1007/s11771-021-4608-y * |
| XI-SHUO WU ET AL.: "Revealing the sodium storage behavior of biomass-derived hard carbon by using pure lignin and cellulose as model precursors", 《RENEWABLE ENERGY》, vol. 189, pages 630 - 638, XP087014085, DOI: 10.1016/j.renene.2022.03.023 * |
| 杨乐;胡明祥;张宏伟;黄正宏;吕瑞涛;: "室温钠离子电池用高性能碳材料研究进展", 化学工业与工程, vol. 36, no. 03, pages 22 - 34 * |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115744871A (en) * | 2022-11-26 | 2023-03-07 | 中南大学 | Bagasse-based sodium ion battery hard carbon negative electrode active material, and preparation and application thereof |
| CN115818634A (en) * | 2022-12-01 | 2023-03-21 | 山西沁新能源集团股份有限公司 | Method for preparing sodium-ion battery negative electrode material by taking cedar as raw material |
| CN116404128A (en) * | 2023-03-30 | 2023-07-07 | 湖北万润新能源科技股份有限公司 | Porous hard carbon anode material and preparation method and application thereof |
| CN117069093A (en) * | 2023-09-15 | 2023-11-17 | 福建省鑫森炭业股份有限公司 | Preparation method of hard carbon anode material |
| CN117069093B (en) * | 2023-09-15 | 2024-06-07 | 福建省鑫森炭业股份有限公司 | Preparation method of hard carbon anode material |
| CN117466278A (en) * | 2023-11-01 | 2024-01-30 | 东北大学 | Method for ball milling modification of hard carbon material and application of ball milling modification of hard carbon material in negative electrode of sodium ion battery |
| CN117466278B (en) * | 2023-11-01 | 2024-05-17 | 东北大学 | Method for ball milling modification of hard carbon material and application of ball milling modification of hard carbon material in negative electrode of sodium ion battery |
| CN117550587A (en) * | 2024-01-11 | 2024-02-13 | 邢台旭阳新能源科技有限公司 | Negative electrode material and preparation method and application thereof |
| CN117550587B (en) * | 2024-01-11 | 2024-03-29 | 邢台旭阳新能源科技有限公司 | Negative electrode material and preparation method and application thereof |
| CN117735527A (en) * | 2024-02-21 | 2024-03-22 | 山东埃尔派粉体科技股份有限公司 | Biomass hard carbon anode material, preparation method thereof and sodium ion battery based on biomass hard carbon anode material |
| CN117735527B (en) * | 2024-02-21 | 2024-05-14 | 山东埃尔派粉体科技股份有限公司 | Biomass hard carbon anode material, preparation method thereof and sodium ion battery based on biomass hard carbon anode material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115020643B (en) | 2024-08-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN115020643B (en) | Hard carbon based on biomass, preparation method thereof and application thereof in sodium ion battery | |
| CN111180691B (en) | Double-layer carbon-coated silicon-based composite material and preparation method and application thereof | |
| CN109004199B (en) | Preparation method of biomass hard carbon material for negative electrode of sodium-ion battery | |
| CN115064667B (en) | Biomass hard carbon based on low crystalline cellulose content and preparation method and application thereof | |
| CN108862235B (en) | Fibrous hollow hard carbon material for sodium ion battery cathode and preparation method thereof | |
| CN112133896B (en) | High-capacity graphite-silicon oxide composite material and preparation method and application thereof | |
| CN108269982B (en) | Composite material, preparation method thereof and application thereof in lithium ion battery | |
| CN109399601B (en) | Preparation method and application of nitrogen-phosphorus co-doped biochar material | |
| CN107919477B (en) | Application of mixed expanded graphite as negative electrode material of lithium ion battery | |
| CN114044513A (en) | Preparation method of coal-based graphite/carbon composite negative electrode material for power type lithium ion battery | |
| CN114551871A (en) | Spherical hard carbon composite material and preparation method and application thereof | |
| CN112928246A (en) | Composite material, preparation method and application thereof | |
| CN113292065A (en) | Large-interlayer-spacing monodisperse nano hard carbon material, and synthesis method and application thereof | |
| CN112670669A (en) | Nitrogen-doped carbon-coated Co and/or Co3Application of ZnC composite material in preparation of lithium-sulfur battery diaphragm | |
| CN115849367B (en) | Sodium ion battery negative electrode material based on natural graphite raw material, preparation method thereof and sodium ion battery | |
| CN116395670A (en) | Preparation method of hard carbon negative electrode material of sodium ion battery | |
| CN114420932B (en) | High-performance glass-ceramic electrode material containing variable-valence metal ion oxide, and preparation method and application thereof | |
| KR20240073848A (en) | Cathode material, battery | |
| CN114804065A (en) | Hard carbon based on alpha-type cellulose material and preparation method and application thereof | |
| CN114094075A (en) | Iron selenide-iron oxide nanotube/graphene aerogel composite anode material and preparation method and application thereof | |
| CN113233440A (en) | Modified preparation method of hard carbon negative electrode material with high first efficiency and long cycle life | |
| CN107959007B (en) | Preparation method of graphene-silicon-coated lithium ion battery negative electrode material | |
| CN111326727A (en) | Multi-component silicon-oxygen negative electrode material for lithium ion battery and preparation method thereof | |
| CN112993247A (en) | High-surface-capacity self-supporting hard carbon cathode and preparation and application thereof | |
| Liu et al. | Biomass-Derived Three-Dimensionally Connected Hierarchical Porous Carbon Framework for Long-Life Lithium–Sulfur Batteries |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |