CN116730319A - Preparation device, preparation method and application of biomass-based hard carbon anode material - Google Patents
Preparation device, preparation method and application of biomass-based hard carbon anode material Download PDFInfo
- Publication number
- CN116730319A CN116730319A CN202310503192.7A CN202310503192A CN116730319A CN 116730319 A CN116730319 A CN 116730319A CN 202310503192 A CN202310503192 A CN 202310503192A CN 116730319 A CN116730319 A CN 116730319A
- Authority
- CN
- China
- Prior art keywords
- biomass
- hard carbon
- modified material
- energy
- carbon anode
- 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.)
- Pending
Links
- 239000002028 Biomass Substances 0.000 title claims abstract description 132
- 229910021385 hard carbon Inorganic materials 0.000 title claims abstract description 114
- 239000010405 anode material Substances 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title claims abstract description 59
- 239000000463 material Substances 0.000 claims abstract description 127
- 238000012986 modification Methods 0.000 claims abstract description 62
- 230000004048 modification Effects 0.000 claims abstract description 62
- 238000000197 pyrolysis Methods 0.000 claims abstract description 39
- 239000013078 crystal Substances 0.000 claims abstract description 34
- 238000003763 carbonization Methods 0.000 claims abstract description 18
- 238000004519 manufacturing process Methods 0.000 claims abstract description 11
- 239000002245 particle Substances 0.000 claims description 121
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 49
- 239000002994 raw material Substances 0.000 claims description 41
- 238000010438 heat treatment Methods 0.000 claims description 40
- 239000012298 atmosphere Substances 0.000 claims description 33
- 238000000034 method Methods 0.000 claims description 30
- 239000003607 modifier Substances 0.000 claims description 21
- 238000004321 preservation Methods 0.000 claims description 20
- 238000003860 storage Methods 0.000 claims description 16
- 239000010439 graphite Substances 0.000 claims description 15
- 229910002804 graphite Inorganic materials 0.000 claims description 15
- 229910052573 porcelain Inorganic materials 0.000 claims description 14
- 150000001450 anions Chemical class 0.000 claims description 13
- 238000001816 cooling Methods 0.000 claims description 13
- 230000001965 increasing effect Effects 0.000 claims description 12
- 238000002347 injection Methods 0.000 claims description 12
- 239000007924 injection Substances 0.000 claims description 12
- 230000007547 defect Effects 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- 230000002708 enhancing effect Effects 0.000 claims description 8
- 238000007873 sieving Methods 0.000 claims description 7
- 229910001415 sodium ion Inorganic materials 0.000 claims description 7
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 6
- 238000009396 hybridization Methods 0.000 claims description 6
- 239000011229 interlayer Substances 0.000 claims description 5
- 150000002500 ions Chemical class 0.000 claims description 5
- 238000002441 X-ray diffraction Methods 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 239000012535 impurity Substances 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 4
- 150000004291 polyenes Chemical class 0.000 claims description 4
- 238000004846 x-ray emission Methods 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 3
- 238000005086 pumping Methods 0.000 claims description 3
- 238000012216 screening Methods 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- 239000003575 carbonaceous material Substances 0.000 abstract description 18
- 125000005842 heteroatom Chemical group 0.000 abstract description 7
- 235000013162 Cocos nucifera Nutrition 0.000 description 69
- 244000060011 Cocos nucifera Species 0.000 description 69
- 229910052799 carbon Inorganic materials 0.000 description 35
- 210000002381 plasma Anatomy 0.000 description 28
- 239000007833 carbon precursor Substances 0.000 description 26
- 239000002296 pyrolytic carbon Substances 0.000 description 20
- 230000008569 process Effects 0.000 description 19
- 239000000498 cooling water Substances 0.000 description 16
- 238000005485 electric heating Methods 0.000 description 15
- 230000000694 effects Effects 0.000 description 14
- 239000007789 gas Substances 0.000 description 14
- 230000009471 action Effects 0.000 description 13
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- 238000002156 mixing Methods 0.000 description 11
- 239000000203 mixture Substances 0.000 description 11
- 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 10
- 230000001681 protective effect Effects 0.000 description 10
- 229910052708 sodium Inorganic materials 0.000 description 10
- 239000011734 sodium Substances 0.000 description 10
- -1 oxygen anion Chemical class 0.000 description 9
- 229910052760 oxygen Inorganic materials 0.000 description 7
- 239000006245 Carbon black Super-P Substances 0.000 description 6
- 239000002033 PVDF binder Substances 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 239000011230 binding agent Substances 0.000 description 6
- 210000004027 cell Anatomy 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 239000011888 foil Substances 0.000 description 6
- 239000003365 glass fiber Substances 0.000 description 6
- 238000000227 grinding Methods 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 239000007773 negative electrode material Substances 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 238000011056 performance test Methods 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000000354 decomposition reaction Methods 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- 239000010419 fine particle Substances 0.000 description 5
- 230000005484 gravity Effects 0.000 description 5
- 239000010903 husk Substances 0.000 description 5
- 238000007789 sealing Methods 0.000 description 5
- 238000005265 energy consumption Methods 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- 230000009257 reactivity Effects 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- 238000006557 surface reaction Methods 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000011362 coarse particle Substances 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 229910000619 316 stainless steel Inorganic materials 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 238000001237 Raman spectrum Methods 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 239000010431 corundum Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 241000609240 Ambelania acida Species 0.000 description 1
- 241001494508 Arundo donax Species 0.000 description 1
- 235000014676 Phragmites communis Nutrition 0.000 description 1
- 241001520913 Phyllostachys edulis Species 0.000 description 1
- 235000003570 Phyllostachys pubescens Nutrition 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 239000010905 bagasse Substances 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910021469 graphitizable carbon Inorganic materials 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000010902 jet-milling Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- GALOTNBSUVEISR-UHFFFAOYSA-N molybdenum;silicon Chemical compound [Mo]#[Si] GALOTNBSUVEISR-UHFFFAOYSA-N 0.000 description 1
- 229910052863 mullite Inorganic materials 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
- B01J19/087—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electric or magnetic energy
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B02—CRUSHING, PULVERISING, OR DISINTEGRATING; PREPARATORY TREATMENT OF GRAIN FOR MILLING
- B02C—CRUSHING, PULVERISING, OR DISINTEGRATING IN GENERAL; MILLING GRAIN
- B02C19/00—Other disintegrating devices or methods
- B02C19/06—Jet mills
-
- 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
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F27—FURNACES; KILNS; OVENS; RETORTS
- F27B—FURNACES, KILNS, OVENS, OR RETORTS IN GENERAL; OPEN SINTERING OR LIKE APPARATUS
- F27B17/00—Furnaces of a kind not covered by any preceding group
-
- 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
- H01M4/36—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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
- B01J2219/0894—Processes carried out in the presence of a plasma
-
- 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
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
-
- 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 invention discloses a preparation device of a biomass-based hard carbon anode material, which comprises the following components: surface distortion systems, high energy surface modification systems, and high temperature carbonization systems. The invention also provides a preparation method for preparing the biomass-based hard carbon anode material by using the preparation device for the biomass-based hard carbon anode material and application of the biomass-based hard carbon anode material prepared by the preparation method. The preparation device and the preparation method of the biomass-based hard carbon anode material are based on the biomass hetero-atom doping modification-high-temperature pyrolysis carbonization principle, and based on the crystal structure characteristics of the hard carbon material, the high-energy surface modification-high-temperature carbonization is combined with the surface distortion of the material, so that the production efficiency can be improved, the production cost can be reduced, and the high-efficiency preparation of the biomass-based amorphous hard carbon anode material can be realized.
Description
Technical Field
The invention belongs to the field of battery materials, and particularly relates to a preparation device, a preparation method and application of a negative electrode material.
Background
Sodium ion batteries are increasingly favored in the energy storage battery market because of limited global lithium resources that cannot meet the demands of power and energy storage lithium batteries. The current sodium ion battery anode material comprises a carbon-based material, a titanium-based material, an alloy material, an organic material and the like, wherein the amorphous hard carbon material is the preferred material of the current sodium ion battery commercial anode material due to the advantages of wide raw material sources, low cost, environmental friendliness, relatively excellent sodium storage performance and the like.
The hard carbon material is a hardly graphitizable carbon material, and is not completely graphitizable even at high temperature (2800 ℃). The interlayer spacing of the graphite of the hard carbon is larger than 0.36nm, the larger interlayer spacing is favorable for intercalation or deintercalation of sodium ions, and a large number of defects and pores exist in the hard carbon, so that a large number of active sodium storage sites are provided, and the hard carbon has higher sodium storage capacity. Biomass raw materials are widely distributed in nature, and biomass raw materials are used as precursors to produce the biomass-based hard carbon material, so that the biomass-based hard carbon material is a good choice.
The preparation method has the advantages that the problems of low production efficiency, difficulty in large-scale production, non-ideal electrochemical performance of the hard carbon material and the like, particularly the problems of low initial coulomb efficiency, low specific capacity and the like cannot be well solved. At present, a preparation method and a device of a biomass-based hard carbon material for improving the crystal structure characteristic of the biomass-based hard carbon material are freshly reported, and a novel preparation method and a novel preparation device of the biomass-based hard carbon negative electrode material are developed based on the crystal structure characteristic of the biomass-based hard carbon material so as to realize efficient and stable production of the biomass-based hard carbon negative electrode material with high specific capacity and high first-effect coulomb efficiency, and have practical significance.
Disclosure of Invention
The invention aims to overcome the defects and the shortcomings in the background art, and provides a preparation device, a preparation method and application of a biomass-based hard carbon anode material with high efficiency and high electrochemical performance. In order to solve the technical problems, the technical scheme provided by the invention is as follows:
a preparation device of biomass-based hard carbon anode material, comprising:
surface distortion system: the method comprises the steps of crushing a biomass raw material airflow, and enhancing the surface lattice distortion degree of the crushed biomass raw material to obtain a first modified material; the surface distortion system comprises an airflow disruption chamber;
high energy surface modification system: the method is used for realizing the surface modification of the first modified material and increasing the disorder degree of crystals to obtain a second modified material; the high-energy surface modification system comprises a high-energy modification chamber and a plasma emission component for ionizing a modification atmosphere in the high-energy modification chamber to obtain anions to modify the first modified material; the surface distortion system is connected with the high-energy surface modification system through an airflow conveying pipe;
high temperature carbonization system: and heating the second modified material in an inert atmosphere to carbonize and crack the second modified material to obtain the biomass-based hard carbon anode material.
In the above preparation device, preferably, the air flow crushing cavity is provided with a feed pipe and a plurality of compressed air pipes, and the inner wall of the air flow crushing cavity is provided with a high-hardness wear-resistant lining; the one end of inlet pipe is equipped with compressed air inlet, the other end with the broken chamber of air current communicates, the inlet pipe is being close to one side of compressed air inlet is equipped with the feed inlet, be equipped with in the inlet pipe one side that is close to the broken chamber of air current Laval nozzle.
In the above preparation device, preferably, a modifier injection port is provided on the high-energy modification chamber, and a storage tank with an observation window is provided at the bottom of the high-energy modification chamber; the plasma emission component comprises a radio frequency emitter and a plasma emission electrode.
In the above preparation device, preferably, the high-temperature carbonization system comprises a movable porcelain boat and a heating furnace tube, wherein the heating furnace tube is connected with a vacuumizing assembly, a heat preservation assembly, an inflating assembly for inflating inert gas during high-temperature carbonization and a cooling assembly for cooling materials.
According to the invention, biomass-based preheating carbon-decomposing particles subjected to mechanical crushing and sieving treatment are added through a feed inlet. Under the drive of high-speed compressed air of a feeding compressed air inlet, biomass-based pre-pyrolytic carbon particles after sieving are further accelerated through a Laval nozzle to reach supersonic speed and enter the inside of a gas-liquid crushing cavity. The cavity wall of the airflow crushing cavity is provided with a plurality of compressed air pipes (namely high-energy compressed air inlets) at the periphery, materials collide with each other, rub and shear under the drive of the rotating airflow, and the materials can be fully crushed. In the crushing process, coarse particles move towards the cavity wall under the action of a larger centrifugal force and collide at the cavity wall to return to have a cyclic crushing effect; the fine particles are concentrated in the central part of the airflow disruption chamber and flow out along the airflow conveying pipe under the action of small centrifugal force. The lining of the airflow crushing cavity is made of a high-hardness and high-wear-resistance material, and the corundum material coated by the nano tungsten carbide material can be adopted in the invention. Meanwhile, the high-energy compressed air drives the high-frequency ultra-high energy collision, impact and friction of the biomass-based pre-pyrolysis particles, so that crystal grains on the surfaces of the biomass-based pre-pyrolysis particles are subjected to lattice distortion, and the reactivity and defects on the surfaces of crystal lattices of the particles are enhanced.
The top of the high-energy modifying chamber of the invention can be provided with a vertical air outlet, and the modifier injection port can be made of 316 stainless steel for injecting modifiers such as O required in the high-energy surface modifying reaction process 2 、NH 3 、CF 4 、H 2 S、N 2 Etc. The first modified material which flows out along with the surface distortion system at high speed moves spirally in the high-energy modification chamber, and the plasma emitting electrode generates plasma beams and ionizes molecules in the atmosphere to obtain anions by adjusting the frequency and the power of the radio frequency generator, so that the anions are opposite to the high surfaceThe first modified material which should be activated reacts to realize further high-energy surface modification of the first modified material. The second modified material subjected to further high-energy surface modification continues to perform spiral movement until the second modified material falls into the storage tank. The left side of the storage tank is provided with a material observation window for observing the storage condition of materials, and when the height of the materials is close to the upper edge of the material observation window, a valve at the bottom of the storage tank can be opened for discharging.
The high-temperature carbonization system comprises a movable porcelain boat and a heating furnace tube, and particularly the movable porcelain boat comprises a high-temperature porcelain boat and a movable boat placing plate, the heating furnace tube comprises a high-temperature furnace tube and electric heating units distributed on the surface of the high-temperature furnace tube, an inflating component comprises an air inlet tube and a horizontal air outlet tube which are positioned on the high-temperature furnace tube, one end of the high-temperature furnace tube is provided with a feeding furnace door cover, the other end of the high-temperature furnace tube is provided with a fixed furnace door cover, the surface of the high-temperature furnace tube is provided with a heat preservation component, the high-temperature furnace tube is connected with a vacuumizing component, and the feeding furnace door cover and the fixed furnace door cover are connected with a cooling component. The high-temperature furnace tube can be made of corundum, the electric heating unit can be preferably made of a silicon-molybdenum rod, the heat preservation component can be made of mullite, and the air inlet tube and the horizontal air outlet tube are made of 316 stainless steel. And heat preservation components are arranged outside the electric heating unit and the high-temperature furnace tube, so that heat loss is reduced, and energy consumption can be effectively saved. The contact interfaces of the feeding furnace door cover, the fixed furnace door cover and the high-temperature furnace tube are provided with sealing rubber rings for sealing treatment, so that high-temperature sample oxidation is avoided. The feeding furnace door cover and the fixed furnace door cover are provided with cooling components (a cooling water inlet and a cooling water outlet) for cooling in a high-temperature process, so that the sealing rubber ring is prevented from being burnt and the safety of operators is ensured. The vacuumizing assembly can be a mechanical pump, and the mechanical pump is used for vacuumizing treatment in the high-temperature furnace tube before heating, so that the crystal form conversion of the sample in an anoxic environment is further ensured; in order to protect equipment and personnel safety in the material preparation process, a mechanical pump is strictly forbidden to be started at 1000 ℃.
As a general technical concept, the present invention also provides a preparation method for preparing a biomass-based hard carbon anode material using the preparation apparatus for a biomass-based hard carbon anode material, comprising the steps of:
s1: pre-pyrolyzing biomass raw materials, and then crushing and screening the biomass raw materials to obtain pretreated raw materials;
s2: feeding the pretreated raw material into an airflow crushing cavity of the surface distortion system, further performing airflow crushing on the pretreated raw material, and enhancing the surface lattice distortion degree of the raw material after further crushing to obtain a first modified material;
s3: feeding the first modified material into a high-energy modification chamber of the high-energy surface modification system through an airflow conveying pipe, adding a modifier into the high-energy modification chamber, and starting the plasma emission assembly to ionize the modifier in the high-energy modification chamber to obtain anions so as to modify the first modified material, so that the crystal disorder degree of the first modified material is increased to obtain a second modified material;
s4: and sending the second modified material into the high-temperature carbonization system, and heating the second modified material in an inert atmosphere to carbonize and crack the second modified material to obtain the biomass-based hard carbon anode material.
In the above preparation method, preferably, the degree of surface lattice distortion of the first modified material is measured by full width at half maximum FWHM of a peak in a XRD pattern of the particle, specifically fwhm=k·d·sin θ, where K is an empirical coefficient, D is a grain size, θ is an X-ray emission angle, and FWHM is controlled to be 0.11 to 0.15.
In the above preparation method, preferably, the second modified material has a crystal disorder degree dd= (I) D1 +I D2 +I D3 +I D4 )/I G Wherein I D1 Sp as the second modifying material 3 Hybridization intensity, I D2 Is the bonding strength of graphite lattice of the second modified material, polyene and impurity ions, I D3 Amorphous graphite lattice strength, I, of the second modified material D4 Surface defect intensity of graphite lattice as second modified material, I G Sp as the second modifying material 2 The hybridization intensity is controlled to be 1.5-2.2.
In the above preparation method, preferably, the pressure of compressed air is controlled to be 0.6-1.0MPa when the airflow is crushed; the modifier comprises O 2 、NH 3 、CF 4 、H 2 S or N 2 And controlling the radio frequency of the plasma emission component to be 20-60MHz and the power to be 200-1000W.
In the preparation method, preferably, the temperature of the pre-pyrolysis is 300-600 ℃, the pre-pyrolysis time is 1-5h, and the size of the control screen is 200-300 meshes when the control screen is screened; when heating under inert atmosphere, the inert atmosphere is nitrogen or argon, the heating rate is controlled to be 1-10 ℃/min, the heat preservation temperature is 1000-1600 ℃, and the heat preservation time is 1-5h.
As a general technical concept, the invention also provides an application of the biomass-based hard carbon anode material prepared by the preparation method, the preparation method of the biomass-based hard carbon anode material is used for the anode of a sodium ion battery, and the interlayer spacing d of the biomass-based hard carbon anode material 002 More than 0.360nm and the particle size is 1-10 mu m.
The biomass feedstock of the present invention may be derived from conventional biomass feedstock: coconut shell, reed, asphalt, phyllostachys pubescens, bagasse, corn cob, arundo donax, and the like.
For better understanding of the invention, the invention provides a preparation method of a hard carbon anode material, which comprises the following steps:
s1: the biomass raw material is subjected to pre-pyrolysis in a muffle furnace filled with inert protective atmosphere at a lower temperature, is kept warm for a certain time and then is cooled to room temperature, and then is subjected to mechanical crushing and sieving treatment to obtain the pretreated raw material.
S2: the screened pretreated feedstock (i.e., biomass-based pre-pyrolytic carbon particles) is added through a feed inlet. And adjusting the air pressure of the feeding compressed air inlet and the compressed air pipe, and enabling biomass-based preheated carbon-decomposing particles to enter the airflow crushing cavity after being accelerated to supersonic speed by the compressed air through a Laval nozzle. In the airflow crushing cavity, biomass-based pre-heated carbon-decomposing particles are driven by high-energy compressed air to collide and impact strongly, and the degree of lattice distortion of the surfaces of the particles is enhanced. At the same time, under strong collision and impact, biomass-based pre-pyrolytic carbon particles are broken. In the crushing process, the coarse biomass-based pre-pyrolytic carbon particles move to the cavity wall of the airflow crushing cavity under the action of centrifugal force, collide with the cavity wall and then return to the center of the cavity, so that cyclic crushing occurs. The biomass pre-pyrolysis carbon particles with surface distortion treatment below a certain particle size can flow out along the airflow input pipe to obtain a first modified material.
S3: the first modifying material (i.e., surface distortion treated biomass-based pre-heated carbon-decomposing particles) flows into the high-energy modifying chamber through the air flow input pipe, and simultaneously, whether additional modifying agent is introduced from the modifying agent injection port or not is selected according to actual conditions, and spiral motion is performed in the modifying agent injection port. And (3) starting a power supply of the radio frequency generator, adjusting the frequency and the power, enhancing the surface activity of the biomass-based preheating carbon-decomposing particles subjected to surface distortion treatment, and ionizing the atmosphere by a plasma beam generated by a plasma emission electrode to obtain anions. The biomass-based pre-pyrolysis carbon particles with the surface distortion treated by the anions can be modified, so that hetero atoms in the biomass-based pre-pyrolysis carbon particles with the surface distortion treated are increased, and biomass-based hard carbon precursor particles with higher disorder degree are obtained, namely the second modified material.
S4: in the high-temperature crystal form conversion stage, a bottom valve of a storage tank is opened, biomass-based hard carbon precursor particles naturally fall into a high Wen Cizhou under the action of gravity, a feeding furnace door cover is opened after materials in the high Wen Cizhou are loaded to the porcelain boat with the volume of 2/3, the feeding furnace door cover, an air inlet pipe and a horizontal air outlet pipe are closed after the materials and a movable boat placing plate are pushed into the center of a constant-temperature area of a high-temperature furnace tube together, and vacuumizing is performed through a mechanical pump. And controlling the electric heating unit to heat up to a certain temperature at a certain heating rate, introducing inert protective atmosphere through the air inlet pipe in the high-temperature process, insulating for a certain time, introducing cooling water into the cooling water pipe, and cooling to room temperature to obtain the biomass-based hard carbon anode material.
More specifically, the preparation method comprises the following steps:
s1: biomass raw materials are subjected to pre-pyrolysis in a muffle furnace filled with inert protective atmosphere at a lower temperature, kept for a certain time, cooled to room temperature, and then subjected to mechanical crushing and sieving treatment. The invention preferably has the pre-pyrolysis temperature of 300-600 ℃, the pre-pyrolysis time of 1-5h and the screen size of 200-300 meshes.
S2: the particle size of the material has a large impact on the pyrolysis process and efficiency. And mechanically crushing and sieving the cooled pre-pyrolysis material, and then precisely crushing by using an air mill to obtain the biomass-based pre-pyrolysis carbon particles with controllable granularity, narrow granularity distribution, smooth particle surface and regular shape and surface distortion treatment. When the particles are damaged by impact, the required power W is shown as the following formula:
wherein sigma is the strength limit of the material, E is the elastic modulus of the material, m is the mass of the material particles, and ρ is the density of the material. In order to achieve the purpose of accurate crushing, the airflow or material speed of the airflow crushing must have a high speed, and large energy is generated during high-speed collision to crush particles. Combining the high-energy compressed air and the Laval nozzle, enabling the gas to enter the contraction section of the Laval nozzle at a certain initial speed, wherein the flow speed of the gas is continuously increased along with the reduction of the section and flows to the throat part; after entering the diverging section of the laval nozzle, the velocity of the transonic airflow increases as the cross-section increases. Therefore, after passing through the Laval nozzle, the airflow and the material particles have ultrahigh kinetic energy and impact force, so that the material particles can be efficiently and accurately crushed, and meanwhile, the crystal grains on the surfaces of the particles can be subjected to lattice distortion by high-speed collision and impact energy, and the reactivity of the lattice surfaces of the particles is enhanced. The degree of distortion of the surface of the particle lattice can be measured by the full width at half maximum FWHM of the (002) peak in the XRD pattern of the particle, specifically fwhm=k·d·sin θ, where K is the empirical factor, D is the grain size, and θ is the X-ray emission angle. The narrower the full width half maximum FWHM, the larger the grain size of the particles, the fewer the particle defects and the smaller the degree of particle distortion.
And adding sieved biomass-based preheating and carbon-decomposing particles through a feed inlet, adjusting the air pressure of feeding compressed air and a compressed air pipe, and enabling the biomass-based preheating and carbon-decomposing particles to enter an airflow crushing cavity after being accelerated to supersonic speed by a Laval nozzle under the pushing of the compressed air. In the airflow crushing cavity, biomass-based pre-heated carbon-decomposing particles are driven by high-energy compressed air to collide and impact strongly, and the degree of lattice distortion of the surfaces of the particles is enhanced. At the same time, under strong collision and impact, biomass-based pre-pyrolytic carbon particles are broken. In the jet milling process, coarse particles move towards the cavity wall due to the fact that the centrifugal force received by the coarse particles is large, and fine particles are small in the centrifugal force received by the fine particles and move towards the center of the cavity, so that only fine particles meeting the particle size requirement flow out along the jet conveying pipe. Therefore, in the crushing process, the coarse biomass-based pre-pyrolytic carbon particles move to the cavity wall of the airflow crushing cavity under the action of centrifugal force, collide with the cavity wall and then return to the center of the cavity, so that cyclic crushing occurs. Surface distortion treated biomass pre-pyrolysis carbon particles below a certain particle size can flow out along the airflow conveying pipe. Considering the energy consumption in the actual preparation process, the compressed air pressure of the air flow fine crushing is 0.6-1.0MPa, the collection of biomass-based pre-heating carbon-decomposing particle powder for surface distortion treatment with fine particle size can be more efficiently realized under the condition, and the full width at half maximum FWHM of the biomass-based pre-heating carbon-decomposing particle for surface distortion treatment can be controlled to be 0.11-0.15.
S3: the extent of defects in the biomass-based hard carbon precursor particles can affect the electrochemical performance of the final hard carbon negative electrode material. Under the drive of high-speed air flow, the biomass-based pre-pyrolysis carbon particles subjected to surface distortion treatment and the modifier introduced by the modifier injection port perform spiral movement in the high-energy modification chamber (the biomass-based pre-pyrolysis carbon particles subjected to surface distortion treatment move under the drive of the high-speed air flow and flow in from the top end side of the high-energy modification chamber, and the cross section of the high-energy modification chamber is circular, so that the air flow performs spiral movement along a curved surface after flowing in, and the material is driven to perform spiral movement). The biomass-based pre-pyrolysis carbon particles subjected to surface distortion treatment have high surface reactivity, so anions obtained by the plasma beam ionization atmosphere can be quickly embedded into a honeycomb network lattice of graphite domains in the biomass-based pre-pyrolysis carbon particles subjected to surface distortion treatment, and high-efficiency and high-energy further surface modification of the biomass-based pre-pyrolysis carbon particles subjected to surface distortion treatment is realized. Disorder degree of high-energy surface-modified biomass-based hard carbon precursor particles(Disorder Degree, DD) is an important parameter for measuring the Degree of order (or Disorder) of crystals of materials, and specifically, the Degree of Disorder DD= (I) D1 +I D2 +I D3 +I D4 )/I G Wherein I D1 Sp as a high energy surface modified biomass-based hard carbon precursor 3 Hybrid (edge defects of graphite lattice), I D2 The bonding strength of graphite lattice, polyene and impurity ions of the biomass-based hard carbon precursor which is high-energy surface modification, I D3 Amorphous graphite lattice strength, I, of a high energy surface modified biomass-based hard carbon precursor D4 Surface defect intensity of graphite lattice of biomass-based hard carbon precursor being high energy surface modified, I G Sp as a high energy surface modified biomass-based hard carbon precursor 2 Hybrid (graphitized) strength. The higher the disorder degree of the high-energy surface modified biomass-based hard carbon precursor particles is, the higher the disorder degree of precursor material crystals is, the amorphous hard carbon anode material is easier to generate in the high-temperature cracking process, and the more active sites for storing sodium are, the higher the specific capacity is.
The biomass-based pre-heated carbon-decomposing particles subjected to surface distortion treatment flow into the high-energy modification chamber through the airflow conveying pipe and do spiral motion in the high-energy modification chamber. And (3) starting a power supply of the radio frequency generator, adjusting the radio frequency to be equal to the power, enhancing the surface activity of the biomass-based pre-heating carbon-decomposing particles subjected to surface distortion treatment, and ionizing the atmosphere by a plasma beam generated by a plasma emission electrode to obtain anions. The anionically modifiable surface-modified biomass-based pre-heat pyrolytic carbon particles cause an increase in heteroatoms in the surface-modified biomass-based pre-heat pyrolytic carbon particles. The energy consumption in the actual preparation process is considered, the radio frequency in the high-energy surface modification process is set to be 20-60MHz, the power is 200-1000W, and the disorder degree of the biomass-based hard carbon precursor particles of the high-energy surface modification can be controlled to be 1.5-2.2.
S4: in the high-temperature crystal form conversion stage, the preparation of the amorphous hard carbon anode material is realized by combining the principle of high-temperature pyrolysis of biomass materials. The biomass-based hard carbon precursor particles obtained through surface distortion treatment and high-energy surface modification treatment are used as hard carbon material precursors, the precursors are subjected to dehydrogenation, degassing and polycondensation in a high-temperature process, the carbon atom framework structure is reserved, and the residual carbon material is the hard carbon material. And (3) placing the biomass-based hard carbon precursor particle powder into a high-temperature tube furnace, introducing inert protective atmosphere, heating to a certain temperature, and preserving heat for a certain time to obtain the hard carbon material. In the actual hard carbon preparation process, the inert protective atmosphere is nitrogen or argon, the heating rate is 1-10 ℃/min, the heat preservation temperature is 1000-1600 ℃, and the heat preservation time is 1-5h. The performance of the hard carbon material may be degraded when the holding temperature is too high. In view of the energy consumption in the actual production process, it is more preferable that the holding temperature is not higher than 1600 ℃.
Compared with the prior art, the invention has the advantages that:
the preparation device and the preparation method of the biomass-based hard carbon anode material are based on the biomass hetero-atom doping modification-high-temperature pyrolysis carbonization principle, are based on the crystal structure characteristics of the hard carbon material, combine with the surface distortion-high-energy surface modification-high-temperature carbonization of the material, accurately crush the pretreated raw materials, and simultaneously utilize the high-speed collision, friction and shearing ultra-high energy driven by high-speed airflow to increase the distortion degree of grains of biomass pre-pyrolysis particles, so that the reactivity of the biomass pre-pyrolysis particles is enhanced, and the biomass pre-pyrolysis particles react with hetero atoms more easily to finish doping. The high-energy surface modification utilizes high-energy plasmas to obtain high-energy charged hetero element ions, hetero atom doping of the first modified material can be completed in a short time, the disordered degree of surface distorted biomass particles is improved, and the second modified material with uniform dimensions is obtained. By the device and the method, the high-efficiency preparation of the biomass-based amorphous hard carbon anode material can be realized while the production efficiency is improved and the production cost is reduced, and the first-time charging specific capacity of the hard carbon anode can reach 348.22 mAh.g under the 0.1C multiplying power -1 The first effect can reach 89.88 percent, and the comprehensive electrochemical performance is excellent.
The preparation device and the preparation method of the biomass-based hard carbon anode material are developed based on the thermodynamic theory analysis, the dynamics strengthening theory and the plasma physical theory of the materials in the hard carbon anode field and combined with the mechanical design and manufacturing basis. The device adopts a longitudinal construction structure, the single component is reasonable in design, and the whole equipment is scientific. The complete equipment has the advantages of small occupied area, high integration level, simple maintenance and the like, can be used for high-energy modification of various biomass-based hard carbon precursors and efficient preparation of hard carbon anode materials, and can effectively solve a plurality of problems of low initial coulomb efficiency, low specific capacity and other electrochemical performances of the existing hard carbon materials.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
Fig. 1 is a schematic structural diagram of a device for preparing a biomass-based hard carbon anode material according to the present invention.
Fig. 2 is a Raman spectrum of the hard carbon precursor material in example 1.
Fig. 3 is a charge-discharge graph of the hard carbon negative electrode material in example 1.
Legend description:
1. a feed inlet; 2. a feed pipe; 3. a laval nozzle; 4. a compressed air tube; 5. a high-hardness wear-resistant lining; 6. an airflow disruption chamber; 7. an air flow conveying pipe; 8. a vertical air outlet; 9. a modifier injection port; 10. a high energy modification chamber; 11. a radio frequency transmitter; 12. a plasma emission electrode; 13. a storage tank; 14. an observation window; 15. a high temperature porcelain boat; 16. a movable boat plate; 17. a feed oven door cover; 18. a high temperature furnace tube; 19. an air inlet pipe; 20. an electric heating unit; 21. a thermal insulation assembly; 22. a cooling water pipe; 23. fixing a furnace door cover; 24. a horizontal air outlet pipe; 25. and (5) vacuumizing the assembly.
Detailed Description
The present invention will be described more fully hereinafter with reference to the accompanying drawings, in which preferred embodiments are shown, for the purpose of illustrating the invention, but the scope of the invention is not limited to the specific embodiments shown.
Unless defined otherwise, all technical and scientific terms used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the scope of the present invention.
Unless otherwise specifically indicated, the various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or may be prepared by existing methods.
Example 1:
as shown in fig. 1, the preparation device of the biomass-based hard carbon anode material of the embodiment includes:
surface distortion system: the method comprises the steps of crushing biomass raw material airflow, and enhancing the surface lattice distortion degree of the crushed biomass raw material to obtain a first modified material; the surface distortion system comprises an airflow disruption chamber 6;
high energy surface modification system: the method is used for realizing the surface modification of the first modified material and increasing the disorder degree of crystals to obtain a second modified material; the high-energy surface modification system comprises a high-energy modification chamber 10 and a plasma emission component for ionizing a modification atmosphere in the high-energy modification chamber 10 to obtain anions to modify the first modified material; the surface distortion system is connected with the high-energy surface modification system through an airflow conveying pipe 7;
high temperature carbonization system: and heating the second modified material in an inert atmosphere to carbonize and crack the second modified material to obtain the biomass-based hard carbon anode material.
In this embodiment, a feeding pipe 2 (the feeding angle may be 45 degrees) and a plurality of compressed air pipes 4 (in this embodiment, the number of compressed air pipes 4 may be specifically 4, and the number of compressed air pipes 4 may be uniformly and horizontally arranged along the outer wall of the airflow crushing cavity 6) are disposed on the airflow crushing cavity 6, and a high-hardness wear-resistant liner 5 is disposed on the inner wall of the airflow crushing cavity 6; one end of the feed pipe 2 is provided with a compressed air inlet, the other end of the feed pipe is communicated with the airflow crushing cavity 6, one side, close to the compressed air inlet, of the feed pipe 2 is provided with a feed inlet 1, and one side, close to the airflow crushing cavity 6, of the feed pipe 2 is internally provided with a Laval nozzle 3.
In the embodiment, a modifier injection port 9 is arranged on a high-energy modification chamber 10, a vertical air outlet 8 is arranged at the top of the high-energy modification chamber 10, and a storage tank 13 with an observation window 14 is arranged at the bottom of the high-energy modification chamber 10; the plasma emission assembly includes a radio frequency emitter 11 and a plasma emission electrode 12.
In this embodiment, the high-temperature carbonization system includes a movable porcelain boat and a heating furnace tube, and the heating furnace tube is connected with a vacuumizing assembly 25, a heat preservation assembly 21, an inflating assembly for inflating inert gas during high-temperature carbonization, and a cooling assembly for cooling materials. Specifically, the movable porcelain boat comprises a high-temperature porcelain boat 15 and a movable boat placing plate 16, the heating furnace tube comprises a high-temperature furnace tube 18 and electric heating units 20 distributed on the surface of the high-temperature furnace tube, the air charging assembly comprises an air inlet tube 19 and a horizontal air outlet tube 24 which are positioned on the high-temperature furnace tube 18, one end of the high-temperature furnace tube 18 is provided with a feeding furnace door cover 17, the other end of the high-temperature furnace tube is provided with a fixed furnace door cover 23, the surface of the high-temperature furnace tube 18 is provided with a heat preservation assembly 21, the high-temperature furnace tube 18 is connected with a vacuumizing assembly 25, and the feeding furnace door cover 17 and the fixed furnace door cover 23 are connected with a cooling assembly. The contact interfaces of the feeding furnace door cover 17, the fixed furnace door cover 23 and the high-temperature furnace tube 18 are provided with sealing rubber rings for sealing treatment to avoid oxidization of the high-temperature sample. The feeding furnace door cover 17 and the fixed furnace door cover 23 are provided with cooling components (cooling water pipes 22) for cooling in the high temperature process. The evacuation assembly 25 may be a mechanical pump.
The preparation device of the biomass-based hard carbon anode material in the embodiment is used for preparing a preparation method of the biomass-based hard carbon anode material, and comprises the following steps:
s1: pre-pyrolyzing biomass raw materials, and then crushing and screening the biomass raw materials to obtain pretreated raw materials;
s2: feeding the pretreated raw material into an airflow crushing cavity 6 of a surface distortion system, further performing airflow crushing on the pretreated raw material, and enhancing the surface lattice distortion degree of the raw material after further crushing to obtain a first modified material;
s3: the first modified material is sent into a high-energy modification chamber 10 of a high-energy surface modification system through an air flow conveying pipe 7, a modifier is added into the high-energy modification chamber 10, and a plasma emission component is started to ionize the modifier in the high-energy modification chamber 10 to obtain anions so as to modify the first modified material, so that the crystal disorder degree of the first modified material is increased to obtain a second modified material;
s4: and (3) sending the second modified material into a high-temperature carbonization system, and heating the second modified material in an inert atmosphere to carbonize and crack the second modified material to obtain the biomass-based hard carbon anode material.
In this embodiment, the degree of surface lattice distortion of the first modified material is measured by FWHM of the full width at half maximum of 002 peak in the XRD pattern of the particle, specifically fwhm=k·d·sin θ, where K is an empirical factor, D is a crystal grain size, θ is an X-ray emission angle, and FWHM is controlled to be 0.11 to 0.15.
In this embodiment, the second modified material has a crystal disorder degree dd= (I) D1 +I D2 +I D3 +I D4 )/I G Wherein I D1 Sp as the second modifying material 3 Hybridization intensity, I D2 Is the bonding strength of graphite lattice of the second modified material, polyene and impurity ions, I D3 Amorphous graphite lattice strength, I, of the second modified material D4 Surface defect intensity of graphite lattice as second modified material, I G Sp as the second modifying material 2 The hybridization intensity is controlled to be 1.5-2.2.
In the embodiment, the pressure of compressed air is controlled to be 0.6-1.0MPa when the airflow is crushed; the modifier comprises O 2 、NH 3 、CF 4 、H 2 S or N 2 The radio frequency of the plasma emission component is controlled to be 20-60MHz, and the power is controlled to be 200-1000W.
In the embodiment, the temperature of the pre-pyrolysis is 300-600 ℃, the pre-pyrolysis time is 1-5h, and the size of the screen is controlled to be 200-300 meshes when the screen is screened; when heating under inert atmosphere, the inert atmosphere is nitrogen or argon, the heating rate is controlled to be 1-10 ℃/min, the heat preservation temperature is 1000-1600 ℃, and the heat preservation time is 1-5h.
The application of the biomass-based hard carbon anode material prepared by the preparation method of the embodiment applies the preparation method of the biomass-based hard carbon anode material to the anode of the sodium ion battery, and the interlayer spacing of the biomass-based hard carbon anode material d 002 More than 0.360nm and the particle size is 1-10 mu m.
Taking coconut shell biomass raw materials as an example, the preparation method of the biomass-based hard carbon anode material comprises the following steps:
s1: 200g of coconut shell biomass raw material is preheated and decomposed for 2 hours at 400 ℃ and then is mechanically crushed, and is screened by a 200-mesh sieve and added with coconut shell pre-pyrolytic carbon through a feed inlet 1. The air pressure of the compressed air on the feeding pipe 2 and the air pressure of the compressed air pipe 4 are regulated to be 0.75MPa, and the coconut shell pre-pyrolysis carbon enters the airflow breaking cavity 6 after being accelerated to supersonic speed by the compressed air through the Laval nozzle 3. In the airflow crushing cavity 6, the coconut shell pre-heating carbon decomposing particles are subjected to strong collision and impact under the drive of high-energy compressed air, the degree of lattice distortion of the particle surfaces is enhanced, and the full width at half maximum FWHM of the (002) crystal face peak of the obtained coconut shell pre-heating carbon decomposing particles subjected to surface distortion is 0.13. At the same time, under strong collision and impact, the coconut shell pre-pyrolysis carbon particles are broken. In the crushing process, the coarse coconut shell pre-pyrolytic carbon particles move to the cavity wall of the airflow crushing cavity 6 under the action of centrifugal force, collide with the high-hardness wear-resistant lining 5 of the cavity wall and then return to the cavity center, so that the coarse coconut shell pre-pyrolytic carbon particles are circularly crushed. The surface-distorted coconut husk pre-heat decarbonized particles below 3 μm flow out along the gas flow duct 7.
S2: the coconut shell pre-heated carbon-decomposing particles subjected to surface distortion treatment flow into the high-energy modification chamber 10 through the air flow conveying pipe 7, and are simultaneously introduced into O through the modifier injection port 9 at a flow rate of 40mL/min 2 And makes a spiral motion therein. The power supply of the radio frequency emitter 11 is started, the frequency is adjusted to be 30MHz, the power is adjusted to be 300W, the surface reaction activity of the coconut shell pre-heated carbon decomposition particles subjected to surface distortion treatment is enhanced, and meanwhile, the plasma beam generated by the plasma emitting electrode 12 enables oxygen in the atmosphere to be ionized to obtain oxyanions. The oxygen anion modified surface distortion treated coconut shell pre-heat carbon decomposition particles increase the C=O and C-O bonds in the coconut shell pre-heat carbon to obtain coconut shell based hard carbon precursor particles with disorder DD of 1.61, and the Raman spectrum of the coconut shell based hard carbon precursor particles is shown in figure 2. Excess gas flows out of the vertical gas outlet 8.
S3: in the high-temperature crystal form conversion stage, the material is used for observingWhen the material level is close to the upper edge of the material observation window 14, the bottom valve of the storage tank 13 is opened, coconut shell-based hard carbon precursor particles naturally fall into the height Wen Cizhou under the action of gravity, after the material in the height Wen Cizhou is loaded to the porcelain boat volume of 2/3, the feeding furnace door cover 17 and the movable boat placing plate 16 are opened and pushed into the center of the constant temperature area of the high-temperature furnace tube 18, the feeding furnace door cover 17, the air inlet pipe 19 on the heat preservation component 21 and the horizontal air outlet pipe 24 on the fixed furnace door cover 23 are closed, and vacuum pumping is performed through a mechanical pump. The electric heating unit 20 is controlled to be heated to 1400 ℃ at the heating rate of 5 ℃/min, and N is introduced into the electric heating unit at the flow rate of 0.3L/min through the air inlet pipe 19 during the high temperature process 2 And (3) after the protective atmosphere is preserved for 2 hours, cooling water is introduced into the cooling water pipe 22, and the temperature is reduced to room temperature, so that the hard carbon anode material is obtained.
Weighing the following components in percentage by mass: 5:5, mixing and grinding the hard carbon anode material of the embodiment with conductive carbon black Super-P and a binder PVDF (polyvinylidene fluoride), dissolving the mixture by using NMP (N-methylpyrrolidone) as a solvent, uniformly mixing, coating the mixture on an aluminum foil to prepare an anode sheet, taking a metal sodium sheet as a positive electrode in a vacuum glove box, taking a battery diaphragm as a glass fiber diaphragm of Whatman GF/D, and taking 1mol/L NaPF as electrolyte 6 (dme=100 Vol), assembled into a button half cell of CR 2032. The electrochemical performance test is carried out in the 0-2V interval under the 0.1C multiplying power, the charge and discharge curves are shown in figure 3, and the figure 3 shows that the first charge specific capacity of the hard carbon anode material is 348.22 mAh.g -1 The first effect is 89.88%.
Example 2:
the apparatus for producing the biomass-based hard carbon anode material of this example was the same as in example 1.
Taking coconut shell biomass raw materials as an example, the preparation method of the biomass-based hard carbon anode material comprises the following steps:
s1: 200g of coconut shell biomass raw material is preheated and decomposed for 2 hours at 400 ℃ and then is mechanically crushed, and is screened by a 200-mesh sieve and added with coconut shell pre-pyrolytic carbon through a feed inlet 1. The air pressure of the compressed air on the feeding pipe 2 and the air pressure of the compressed air pipe 4 are regulated to be 0.75MPa, and the coconut shell pre-pyrolysis carbon enters the airflow breaking cavity 6 after being accelerated to supersonic speed by the compressed air through the Laval nozzle 3. In the airflow crushing cavity 6, the coconut shell pre-heating carbon decomposing particles are subjected to strong collision and impact under the drive of high-energy compressed air, the degree of lattice distortion of the particle surfaces is enhanced, and the full width at half maximum FWHM of the (002) crystal face peak of the obtained coconut shell pre-heating carbon decomposing particles subjected to surface distortion is 0.13. At the same time, under strong collision and impact, the coconut shell pre-pyrolysis carbon particles are broken. In the crushing process, the coarse coconut shell pre-pyrolytic carbon particles move to the cavity wall of the airflow crushing cavity 6 under the action of centrifugal force, collide with the high-hardness wear-resistant lining 5 of the cavity wall and then return to the cavity center, so that the coarse coconut shell pre-pyrolytic carbon particles are circularly crushed. The surface-distorted coconut husk pre-heat decarbonized particles below 3 μm flow out along the gas flow duct 7.
S2: the coconut shell pre-heated carbon-decomposing particles subjected to surface distortion treatment flow into the high-energy modification chamber 10 through the air flow conveying pipe 7, and are simultaneously introduced into O through the modifier injection port 9 at a flow rate of 40mL/min 2 And makes a spiral motion therein. The power supply of the radio frequency emitter 11 is started, the frequency is adjusted to be 30MHz, the power is adjusted to be 300W, the surface reaction activity of the coconut shell pre-heated carbon decomposition particles subjected to surface distortion treatment is enhanced, and meanwhile, the plasma beam generated by the plasma emitting electrode 12 enables oxygen in the atmosphere to be ionized to obtain oxyanions. The oxygen anions modify the surface distortion treated coconut shell pre-heat carbonised particles such that the c=o and C-O bonds in the coconut shell pre-heat carbonised are increased to give coconut shell based hard carbon precursor particles having a disorder DD of 1.61 and excess gas flows out of the vertical gas outlet 8.
S3: in the high-temperature crystal form conversion stage, the material level is observed in real time through the material observation window 14, when the material level is close to the upper edge of the material observation window 14, the bottom valve of the storage tank 13 is opened, coconut shell-based hard carbon precursor particles naturally fall into the high Wen Cizhou under the action of gravity, after the material in the high Wen Cizhou is loaded to the porcelain boat volume of 2/3, the feeding furnace door cover 17 and the movable boat placing plate 16 are opened and pushed into the center of a constant temperature area of the high-temperature furnace tube 18, the feeding furnace door cover 17, the air inlet pipe 19 on the heat preservation assembly 21 and the horizontal air outlet pipe 24 on the fixed furnace door cover 23 are closed, and vacuumizing is performed through a mechanical pump. Controlling the electric heating unit 20 to 5 DEG C The temperature rising rate per min is increased to 1200 ℃, and N is introduced into the high-temperature furnace through the air inlet pipe 19 at the flow rate of 0.3L/min 2 And (3) after the protective atmosphere is preserved for 2 hours, cooling water is introduced into the cooling water pipe 22, and the temperature is reduced to room temperature, so that the hard carbon anode material is obtained.
Weighing the following components in percentage by mass: 5:5, mixing and grinding the hard carbon anode material of the embodiment with conductive carbon black Super-P and a binder PVDF (polyvinylidene fluoride), dissolving the mixture by using NMP (N-methylpyrrolidone) as a solvent, uniformly mixing, coating the mixture on an aluminum foil to prepare an anode sheet, taking a metal sodium sheet as a positive electrode in a vacuum glove box, taking a battery diaphragm as a glass fiber diaphragm of Whatman GF/D, and taking 1mol/L NaPF as electrolyte 6 (dme=100 Vol), assembled into a button half cell of CR 2032. Electrochemical performance test is carried out in the range of 0-2V under the multiplying power of 0.1C, and the initial charge specific capacity is 322.28 mAh.g -1 The first effect is 85.94%.
Example 3:
the apparatus for producing the biomass-based hard carbon anode material of this example was the same as in example 1.
Taking coconut shell biomass raw materials as an example, the preparation method of the biomass-based hard carbon anode material comprises the following steps:
s1: 200g of coconut shell biomass raw material is preheated and decomposed for 2 hours at 400 ℃ and then is mechanically crushed, and is screened by a 200-mesh sieve and added with coconut shell pre-pyrolytic carbon through a feed inlet 1. The air pressure of the compressed air on the feeding pipe 2 and the air pressure of the compressed air pipe 4 are regulated to be 0.75MPa, and the coconut shell pre-pyrolysis carbon enters the airflow breaking cavity 6 after being accelerated to supersonic speed by the compressed air through the Laval nozzle 3. In the airflow crushing cavity 6, the coconut shell pre-heating carbon decomposing particles are subjected to strong collision and impact under the drive of high-energy compressed air, the degree of lattice distortion of the particle surfaces is enhanced, and the full width at half maximum FWHM of the (002) crystal face peak of the obtained coconut shell pre-heating carbon decomposing particles subjected to surface distortion is 0.13. At the same time, under strong collision and impact, the coconut shell pre-pyrolysis carbon particles are broken. In the crushing process, the coarse coconut shell pre-pyrolytic carbon particles move to the cavity wall of the airflow crushing cavity 6 under the action of centrifugal force, collide with the high-hardness wear-resistant lining 5 of the cavity wall and then return to the cavity center, so that the coarse coconut shell pre-pyrolytic carbon particles are circularly crushed. The surface-distorted coconut husk pre-heat decarbonized particles below 3 μm flow out along the gas flow duct 7.
S2: the coconut shell pre-heated carbon-decomposing particles subjected to surface distortion treatment flow into the high-energy modification chamber 10 through the air flow conveying pipe 7, and are simultaneously introduced into O through the modifier injection port 9 at a flow rate of 40mL/min 2 And makes a spiral motion therein. The power supply of the radio frequency emitter 11 is started, the frequency is adjusted to be 30MHz, the power is adjusted to be 300W, the surface reaction activity of the coconut shell pre-heated carbon decomposition particles subjected to surface distortion treatment is enhanced, and meanwhile, the plasma beam generated by the plasma emitting electrode 12 enables oxygen in the atmosphere to be ionized to obtain oxyanions. The oxygen anions modify the surface distortion treated coconut shell pre-heat carbonised particles such that the c=o and C-O bonds in the coconut shell pre-heat carbonised are increased to give coconut shell based hard carbon precursor particles having a disorder DD of 1.61 and excess gas flows out of the vertical gas outlet 8.
S3: in the high-temperature crystal form conversion stage, the material level is observed in real time through the material observation window 14, when the material level is close to the upper edge of the material observation window 14, the bottom valve of the storage tank 13 is opened, coconut shell-based hard carbon precursor particles naturally fall into the high Wen Cizhou under the action of gravity, after the material in the high Wen Cizhou is loaded to the porcelain boat volume of 2/3, the feeding furnace door cover 17 and the movable boat placing plate 16 are opened and pushed into the center of a constant temperature area of the high-temperature furnace tube 18, the feeding furnace door cover 17, the air inlet pipe 19 on the heat preservation assembly 21 and the horizontal air outlet pipe 24 on the fixed furnace door cover 23 are closed, and vacuumizing is performed through a mechanical pump. The electric heating unit 20 is controlled to be heated to 1000 ℃ at the heating rate of 5 ℃/min, and N is introduced into the electric heating unit at the flow rate of 0.3L/min through the air inlet pipe 19 during the high temperature process 2 And (3) after the protective atmosphere is preserved for 2 hours, cooling water is introduced into the cooling water pipe 22, and the temperature is reduced to room temperature, so that the hard carbon anode material is obtained.
Weighing the following components in percentage by mass: 5:5, mixing and grinding the hard carbon anode material of the embodiment with conductive carbon black Super-P and a binder PVDF (polyvinylidene fluoride), dissolving the mixture by using NMP (N-methylpyrrolidone) as a solvent, uniformly mixing, coating the mixture on an aluminum foil to prepare an anode sheet, taking a metal sodium sheet as a positive electrode in a vacuum glove box, taking a battery diaphragm as a glass fiber diaphragm of Whatman GF/D, and taking 1mol/L N of electrolyteaPF 6 (dme=100 Vol), assembled into a button half cell of CR 2032. Electrochemical performance test is carried out in the range of 0-2V under the multiplying power of 0.1C, and the initial charge specific capacity is 296.95 mAh.g -1 The first effect is 82.97%.
Example 4:
the apparatus for producing the biomass-based hard carbon anode material of this example was the same as in example 1.
Taking coconut shell biomass raw materials as an example, the preparation method of the biomass-based hard carbon anode material comprises the following steps:
s1: 200g of coconut shell biomass raw material is preheated and decomposed for 2 hours at 400 ℃ and then is mechanically crushed, and is screened by a 200-mesh sieve and added with coconut shell pre-pyrolytic carbon through a feed inlet 1. The air pressure of the compressed air on the feeding pipe 2 and the air pressure of the compressed air pipe 4 are regulated to be 0.75MPa, and the coconut shell pre-pyrolysis carbon enters the airflow breaking cavity 6 after being accelerated to supersonic speed by the compressed air through the Laval nozzle 3. In the airflow crushing cavity 6, the coconut shell pre-heating carbon decomposing particles are subjected to strong collision and impact under the drive of high-energy compressed air, the degree of lattice distortion of the particle surfaces is enhanced, and the full width at half maximum FWHM of the (002) crystal face peak of the obtained coconut shell pre-heating carbon decomposing particles subjected to surface distortion is 0.13. At the same time, under strong collision and impact, the coconut shell pre-pyrolysis carbon particles are broken. In the crushing process, the coarse coconut shell pre-pyrolytic carbon particles move to the cavity wall of the airflow crushing cavity 6 under the action of centrifugal force, collide with the high-hardness wear-resistant lining 5 of the cavity wall and then return to the cavity center, so that the coarse coconut shell pre-pyrolytic carbon particles are circularly crushed. The surface-distorted coconut husk pre-heat decarbonized particles below 3 μm flow out along the gas flow duct 7.
S2: the coconut shell preheated carbon-decomposing particles subjected to surface distortion treatment flow into the high-energy modification chamber 10 through the air flow conveying pipe 7, and simultaneously NH is introduced through the modifier injection port 9 at a flow rate of 40mL/min 3 And makes a spiral motion therein. The power of the radio frequency emitter 11 is turned on, the frequency is adjusted to be 30MHz, the power is adjusted to be 300W, the surface reaction activity of the coconut shell pre-heated carbon decomposition particles subjected to surface distortion treatment is enhanced, and meanwhile, the plasma beam generated by the plasma emitting electrode 12 enables the atmosphere to be ionized to obtain anions. Anionically modifiable surface aberrationsThe treated coconut shell pre-heats the carbon-decomposing particles such that the coconut shell pre-pyrolyzed carbon heteroatoms are increased, resulting in coconut shell-based hard carbon precursor particles with an disorder DD of 1.76, while the excess gas flows out of the vertical gas outlet 8.
S3: in the high-temperature crystal form conversion stage, the material level is observed in real time through the material observation window 14, when the material level is close to the upper edge of the material observation window 14, the bottom valve of the storage tank 13 is opened, coconut shell-based hard carbon precursor particles naturally fall into the high Wen Cizhou under the action of gravity, after the material in the high Wen Cizhou is loaded to the porcelain boat volume of 2/3, the feeding furnace door cover 17 and the movable boat placing plate 16 are opened and pushed into the center of a constant temperature area of the high-temperature furnace tube 18, the feeding furnace door cover 17, the air inlet pipe 19 on the heat preservation assembly 21 and the horizontal air outlet pipe 24 on the fixed furnace door cover 23 are closed, and vacuumizing is performed through a mechanical pump. The electric heating unit 20 is controlled to be heated to 1400 ℃ at the heating rate of 5 ℃/min, and N is introduced into the electric heating unit at the flow rate of 0.3L/min through the air inlet pipe 19 during the high temperature process 2 And (3) after the protective atmosphere is preserved for 2 hours, cooling water is introduced into the cooling water pipe 22, and the temperature is reduced to room temperature, so that the hard carbon anode material is obtained.
Weighing the following components in percentage by mass: 5:5, mixing and grinding the hard carbon anode material of the embodiment with conductive carbon black Super-P and a binder PVDF (polyvinylidene fluoride), dissolving the mixture by using NMP (N-methylpyrrolidone) as a solvent, uniformly mixing, coating the mixture on an aluminum foil to prepare an anode sheet, taking a metal sodium sheet as a positive electrode in a vacuum glove box, taking a battery diaphragm as a glass fiber diaphragm of Whatman GF/D, and taking 1mol/L NaPF as electrolyte 6 (dme=100 Vol), assembled into a button half cell of CR 2032. Electrochemical performance test is carried out in the range of 0-2V under the multiplying power of 0.1C, and the initial charge specific capacity is 371.06 mAh.g -1 The first effect is 86.23%.
Comparative example 1:
compared with example 3, the high-energy surface modification in S2 is not performed after S1 is performed in the comparative example, so that coconut shell-based hard carbon precursor particles with the disorder degree DD of 1.33 are obtained, and then high-temperature crystal form conversion in S3 is directly performed, so that the hard carbon anode material is obtained.
Weighing the following components in percentage by mass: 5:5, the hard carbon negative electrode material and the conductive carbon black of the present pair of examplesMixing and grinding Super-P and a binder PVDF (polyvinylidene fluoride), dissolving the mixture by using NMP (N-methyl pyrrolidone) as a solvent, uniformly mixing, coating on an aluminum foil to prepare a negative plate, taking a metal sodium plate as a positive electrode in a vacuum glove box, taking a battery diaphragm as a glass fiber diaphragm of Whatman GF/D, and taking 1mol/L NaPF as electrolyte 6 (dme=100 Vol), assembled into a button half cell of CR 2032. Electrochemical performance test is carried out in the range of 0-2V under the multiplying power of 0.1C, and the initial charge specific capacity is 267.40 mAh.g -1 The first effect is 80.46%.
Comparative example 2:
compared with the embodiment 3, in the comparative example, the pre-heated carbon solution with the pre-treated and disordered DD of 1.18 is directly used as a hard carbon precursor, and then the high-temperature crystal form conversion in the S3 is directly carried out to obtain the hard carbon anode material, which comprises the following steps:
200g of coconut shell biomass raw material is preheated and decomposed for 2 hours at 400 ℃, then is mechanically crushed, and is directly subjected to high-temperature crystal form conversion after being screened by a 200-mesh sieve. The coconut husk pre-pyrolysis particles subjected to mechanical crushing and sieving treatment are loaded to 2/3 of the volume of a height Wen Cizhou, a feeding furnace door cover 17 and a movable boat plate 16 are opened and pushed into the center of a constant temperature area of a high-temperature furnace tube 18, then the feeding furnace door cover 17, an air inlet pipe 19 on a heat preservation assembly 21 and a horizontal air outlet pipe 24 on a fixed furnace door cover 23 are closed, and vacuum pumping is performed through a mechanical pump. The electric heating unit 20 is controlled to be heated to 1000 ℃ at the heating rate of 5 ℃/min, and N is introduced into the electric heating unit at the flow rate of 0.3L/min through the air inlet pipe 19 during the high temperature process 2 And (3) after the protective atmosphere is preserved for 2 hours, cooling water is introduced into the cooling water pipe 22, and the temperature is reduced to room temperature, so that the hard carbon anode material is obtained.
Weighing the following components in percentage by mass: 5:5, mixing and grinding the hard carbon anode material of the comparative example with conductive carbon black Super-P and a binder PVDF (polyvinylidene fluoride), dissolving the mixture by using NMP (N-methylpyrrolidone) as a solvent, uniformly mixing, coating the mixture on an aluminum foil to prepare an anode sheet, taking a metal sodium sheet as a positive electrode in a vacuum glove box, taking a battery diaphragm as a glass fiber diaphragm of Whatman GF/D, and taking 1mol/L NaPF as electrolyte 6 (dme=100 Vol), assembled into a button half cell of CR 2032. Electrochemical performance test is carried out in the range of 0-2V under the magnification of 0.1C, the firstThe secondary charging specific capacity is 250.67 mAh.g -1 The first effect is 75.34%.
Claims (10)
1. The preparation device of the biomass-based hard carbon anode material is characterized by comprising:
surface distortion system: the method comprises the steps of crushing a biomass raw material airflow, and enhancing the surface lattice distortion degree of the crushed biomass raw material to obtain a first modified material; the surface distortion system comprises an airflow disruption chamber (6);
high energy surface modification system: the method is used for realizing the surface modification of the first modified material and increasing the disorder degree of crystals to obtain a second modified material; the high-energy surface modification system comprises a high-energy modification chamber (10) and a plasma emission component for ionizing a modification atmosphere in the high-energy modification chamber (10) to obtain anions to modify the first modified material; the surface distortion system is connected with the high-energy surface modification system through an airflow conveying pipe (7);
High temperature carbonization system: and heating the second modified material in an inert atmosphere to carbonize and crack the second modified material to obtain the biomass-based hard carbon anode material.
2. The preparation device according to claim 1, characterized in that the air flow crushing cavity (6) is provided with a feed pipe (2) and a plurality of compressed air pipes (4), and the inner wall of the air flow crushing cavity (6) is provided with a high-hardness wear-resistant lining (5); one end of the feed pipe (2) is provided with a compressed air inlet, the other end of the feed pipe is communicated with the airflow crushing cavity (6), one side, close to the compressed air inlet, of the feed pipe (2) is provided with a feed inlet (1), and one side, close to the airflow crushing cavity (6), of the feed pipe (2) is internally provided with a Laval nozzle (3).
3. The preparation device according to claim 1, characterized in that the high-energy modification chamber (10) is provided with a modifier injection port (9), and the bottom of the high-energy modification chamber (10) is provided with a storage tank (13) with an observation window (14); the plasma emission component comprises a radio frequency emitter (11) and a plasma emission electrode (12).
4. A preparation device according to any one of claims 1-3, characterized in that the high temperature carbonization system comprises a movable porcelain boat and a heating furnace tube, wherein a vacuum pumping assembly (25), a heat preservation assembly (21), an air charging assembly for charging inert gas during high temperature carbonization and a cooling assembly for material cooling are connected to the heating furnace tube.
5. A production method for producing a biomass-based hard carbon anode material using the production apparatus for a biomass-based hard carbon anode material according to any one of claims 1 to 4, characterized by comprising the steps of:
s1: pre-pyrolyzing biomass raw materials, and then crushing and screening the biomass raw materials to obtain pretreated raw materials;
s2: feeding the pretreated raw material into an airflow crushing cavity (6) of the surface distortion system, further performing airflow crushing on the pretreated raw material, and enhancing the surface lattice distortion degree of the raw material after further crushing to obtain a first modified material;
s3: feeding the first modified material into a high-energy modification chamber (10) of the high-energy surface modification system through an airflow conveying pipe (7), adding a modifier into the high-energy modification chamber (10), and starting the plasma emission component to ionize the modifier in the high-energy modification chamber (10) to obtain anions so as to modify the first modified material, so that the crystal disorder degree of the first modified material is increased to obtain a second modified material;
s4: and sending the second modified material into the high-temperature carbonization system, and heating the second modified material in an inert atmosphere to carbonize and crack the second modified material to obtain the biomass-based hard carbon anode material.
6. The method according to claim 5, wherein the degree of surface lattice distortion of the first modified material is measured by full width at half maximum FWHM of (002) peak in the XRD pattern of the particles, specifically fwhm=k.d.sin θ, where K is an empirical factor, D is a crystal grain size, θ is an X-ray emission angle, and FWHM is controlled to be 0.11 to 0.15.
7. The method according to claim 5, wherein the second modified material has a crystal disorder degree dd= (I) D1 +I D2 +I D3 +I D4 )/I G Wherein I D1 Sp as the second modifying material 3 Hybridization intensity, I D2 Is the bonding strength of graphite lattice of the second modified material, polyene and impurity ions, I D3 Amorphous graphite lattice strength, I, of the second modified material D4 Surface defect intensity of graphite lattice as second modified material, I G Sp as the second modifying material 2 The hybridization intensity is controlled to be 1.5-2.2.
8. The production method according to any one of claims 5 to 7, wherein the pressure of the compressed air is controlled to be 0.6 to 1.0MPa when the air stream is crushed; the modifier comprises O 2 、NH 3 、CF 4 、H 2 S or N 2 And controlling the radio frequency of the plasma emission component to be 20-60MHz and the power to be 200-1000W.
9. The method according to any one of claims 5 to 7, wherein the temperature of the pre-pyrolysis is 300 to 600 ℃, the time of the pre-pyrolysis is 1 to 5 hours, and the screen size is controlled to be 200 to 300 mesh by sieving; when heating under inert atmosphere, the inert atmosphere is nitrogen or argon, the heating rate is controlled to be 1-10 ℃/min, the heat preservation temperature is 1000-1600 ℃, and the heat preservation time is 1-5h.
10. Use of the biomass-based hard carbon anode material prepared by the preparation method according to any one of claims 5 to 9, wherein the preparation method of the biomass-based hard carbon anode material is used for an anode of a sodium ion battery, and an interlayer spacing d of the biomass-based hard carbon anode material 002 More than 0.360nm and the particle size is 1-10 mu m.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310503192.7A CN116730319A (en) | 2023-05-06 | 2023-05-06 | Preparation device, preparation method and application of biomass-based hard carbon anode material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310503192.7A CN116730319A (en) | 2023-05-06 | 2023-05-06 | Preparation device, preparation method and application of biomass-based hard carbon anode material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116730319A true CN116730319A (en) | 2023-09-12 |
Family
ID=87910517
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310503192.7A Pending CN116730319A (en) | 2023-05-06 | 2023-05-06 | Preparation device, preparation method and application of biomass-based hard carbon anode material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116730319A (en) |
-
2023
- 2023-05-06 CN CN202310503192.7A patent/CN116730319A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110615423B (en) | Preparation method of silicon-based composite negative electrode material of lithium battery | |
| EP2650955B1 (en) | Negative electrode material for lithium ion secondary batteries, and method for producing same | |
| JP6210143B1 (en) | Positive electrode material for lithium ion secondary battery, positive electrode for lithium ion secondary battery, lithium ion secondary battery | |
| KR20210153710A (en) | Silica granules for electrode materials and their manufacturing method and application | |
| CN112952054B (en) | Silicon-based anode material, preparation method thereof, anode and lithium ion battery | |
| CN103794788A (en) | Surface carbon coating method of lithium iron phosphate positive electrode material | |
| CN113479860B (en) | SbPO (styrene-ethylene-propylene-diene monomer) 4 Preparation method of nitrogen-doped carbon composite material | |
| KR20170046114A (en) | Negative active material for lithium secondary battery, method for preparing the same and lithium secondary battery comprising thereof | |
| CN108172791B (en) | Composite negative electrode material, preparation method thereof and lithium ion battery | |
| CN111048785A (en) | Negative electrode material, preparation method thereof, electrode plate and battery | |
| CN108807903B (en) | Preparation method of composite modified lithium battery negative electrode material for lithium battery | |
| JP2022095866A (en) | Anode material for nonaqueous secondary battery, anode for nonaqueous secondary battery, and nonaqueous secondary battery | |
| CN116730319A (en) | Preparation device, preparation method and application of biomass-based hard carbon anode material | |
| CN112151767B (en) | Method for preparing lithium battery cathode by compounding silicon-carbon-silicon dioxide in extruder | |
| KR101104237B1 (en) | Negative composition for Lithium secondary battery using lithium vanadium oxide and manufacturing method thereof | |
| KR20210027328A (en) | Negative active material for lithium secondary battery, method for preparing the same and lithium secondary battery comprising thereof | |
| CN116943571A (en) | Preparation device and preparation method of amorphous hard carbon anode material | |
| JPH09320590A (en) | Lithium ton secondary battery negative electrode material and its manufacture | |
| CN116565199B (en) | Composite particles of carbon negative electrode material of sodium ion battery and preparation method and device thereof | |
| KR20220087143A (en) | Negative electrode material for lithium ion secondary battery, preparation method thereof, and lithium ion secondary battery comprising same | |
| KR20170008056A (en) | Negative active material for lithium secondary battery, method for preparing the same and lithium secondary battery comprising thereof | |
| JP6885503B1 (en) | Positive electrode material for lithium ion secondary batteries, positive electrode for lithium ion secondary batteries, lithium ion secondary batteries | |
| CN113479858B (en) | Composite material for high-performance alkali metal ion battery cathode | |
| EP2151881B1 (en) | Negative electrode material for lithium rechargeable battery | |
| CN117174841A (en) | Composite lithium storage material for lithium ion battery, preparation method and application |
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 |