CN117550587A - Negative electrode material and preparation method and application thereof - Google Patents
Negative electrode material and preparation method and application thereof Download PDFInfo
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- CN117550587A CN117550587A CN202410038508.4A CN202410038508A CN117550587A CN 117550587 A CN117550587 A CN 117550587A CN 202410038508 A CN202410038508 A CN 202410038508A CN 117550587 A CN117550587 A CN 117550587A
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- biomass
- negative electrode
- electrode material
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- 239000007773 negative electrode material Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000002028 Biomass Substances 0.000 claims abstract description 69
- 238000010438 heat treatment Methods 0.000 claims abstract description 55
- 239000004005 microsphere Substances 0.000 claims abstract description 30
- LFTLOKWAGJYHHR-UHFFFAOYSA-N N-methylmorpholine N-oxide Chemical compound CN1(=O)CCOCC1 LFTLOKWAGJYHHR-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000010405 anode material Substances 0.000 claims abstract description 28
- 239000002243 precursor Substances 0.000 claims abstract description 28
- 239000007864 aqueous solution Substances 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 20
- 238000001035 drying Methods 0.000 claims abstract description 15
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 238000001914 filtration Methods 0.000 claims abstract description 11
- 239000000243 solution Substances 0.000 claims abstract description 11
- 238000003763 carbonization Methods 0.000 claims abstract description 3
- 229910001415 sodium ion Inorganic materials 0.000 claims description 18
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 14
- 239000002245 particle Substances 0.000 claims description 12
- 238000010000 carbonizing Methods 0.000 claims description 10
- 238000004321 preservation Methods 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims 3
- 230000008569 process Effects 0.000 abstract description 10
- 239000000463 material Substances 0.000 abstract description 8
- 230000002195 synergetic effect Effects 0.000 abstract description 4
- 238000001338 self-assembly Methods 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 28
- 229910052757 nitrogen Inorganic materials 0.000 description 14
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 12
- 239000000203 mixture Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 238000001027 hydrothermal synthesis Methods 0.000 description 8
- 235000017060 Arachis glabrata Nutrition 0.000 description 7
- 244000105624 Arachis hypogaea Species 0.000 description 7
- 235000010777 Arachis hypogaea Nutrition 0.000 description 7
- 235000018262 Arachis monticola Nutrition 0.000 description 7
- 235000020232 peanut Nutrition 0.000 description 7
- 229910052786 argon Inorganic materials 0.000 description 6
- 238000010335 hydrothermal treatment Methods 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 239000003575 carbonaceous material Substances 0.000 description 4
- 239000011889 copper foil Substances 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 239000013543 active substance Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 229910021385 hard carbon Inorganic materials 0.000 description 3
- 230000005012 migration Effects 0.000 description 3
- 238000013508 migration Methods 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 244000060011 Cocos nucifera Species 0.000 description 2
- 235000013162 Cocos nucifera Nutrition 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 240000007594 Oryza sativa Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- 241000353135 Psenopsis anomala Species 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
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- 239000011248 coating agent Substances 0.000 description 2
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- QEWYKACRFQMRMB-UHFFFAOYSA-N fluoroacetic acid Chemical compound OC(=O)CF QEWYKACRFQMRMB-UHFFFAOYSA-N 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 229920005610 lignin Polymers 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 238000004904 shortening Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- 244000144730 Amygdalus persica Species 0.000 description 1
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 1
- 235000017491 Bambusa tulda Nutrition 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 229920002488 Hemicellulose Polymers 0.000 description 1
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- 229920002472 Starch Polymers 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- 244000269722 Thea sinensis Species 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 235000021307 Triticum Nutrition 0.000 description 1
- 244000098338 Triticum aestivum Species 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
- 239000011425 bamboo Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 229910021384 soft carbon Inorganic materials 0.000 description 1
- 238000011895 specific detection Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- -1 transition metal sulfides Chemical class 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention belongs to the technical field of battery materials, and particularly discloses a negative electrode material, and a preparation method and application thereof. The preparation method provided by the invention comprises the following steps: uniformly mixing biomass and an N-methylmorpholine-N-oxide aqueous solution, heating to 80-150 ℃, and then preserving heat to obtain a biomass reaction solution; heating the biomass reaction liquid to 350-450 ℃, preserving heat under 1.5-3 MPa, filtering, and drying to obtain hydrothermal precursor microspheres; and heating the hydrothermal precursor microsphere to 600-800 ℃ to carry out carbonization reaction, thus obtaining the anode material. According to the invention, the microsphere structure containing more micropore channels is formed by the anode material by utilizing the synergistic effect of the N-methylmorpholine-N-oxide aqueous solution on the biomass treatment combined with the hydrothermal self-assembly process, so that the processability of the anode material is improved, the first coulomb efficiency of the battery is improved, and the multiplying power and the cycle performance of the battery core are improved.
Description
Technical Field
The invention belongs to the technical field of battery materials, and particularly relates to a negative electrode material, and a preparation method and application thereof.
Background
The sodium ion battery has similar physical and chemical properties as the lithium ion battery, has the advantages of lower cost, better safety performance, rich resources, environmental friendliness and the like, and becomes a substitute of the lithium ion battery, and the commercialization of the sodium ion battery also achieves staged results at present. Since the radius of sodium ions is greatly different from that of lithium ions, the conventional negative electrode material for lithium ion batteries is not suitable for sodium ion batteries.
At present, in the research of the cathode electrode material of the sodium ion battery, the carbon-based material and the titanium-based oxide are used as the intercalation and deintercalation type material, and have the advantages of simple preparation, wide sources and low price, but the gram capacity is generally lower; therefore, transition metal oxides, transition metal sulfides and transition metal phosphides are important in the development of transition type negative electrodes, and have the advantages of high specific capacity and excellent performance, but have certain problems, such as large structural expansion of materials due to charge and discharge, easy pulverization and poor circulation; the conventional 14A and 15A main group element and binary metal alloy has the advantages of high gram capacity and good conductivity, but also has the defect of large change of charge and discharge volume. Therefore, searching for new materials with low price, good conductivity and good energy storage is the current commercialized development direction.
The carbon-based material can be basically divided into graphite, soft carbon, hard carbon and the like, and in the research of commercial electrode materials, the hard carbon material prepared by taking biomass as a carbon source has the advantages of rich resource reserves, environmental friendliness and the like, shows wide market prospect, and is also the first choice material of the current commercial sodium ion battery anode material. However, in the practical product application process, the biomass hard carbon material has the defects of poor multiplying power performance, generally low initial coulombic efficiency and the like, and influences the whole electric performance exertion and commercialization process of the sodium ion battery. Therefore, the negative electrode material with low cost is provided, so that the problems of low sodium storage capacity, poor first coulombic efficiency, poor rate capability and poor cycle performance of the existing negative electrode material of the sodium-ion battery are solved.
Disclosure of Invention
In view of the above, the invention provides a negative electrode material, and a preparation method and application thereof. Aiming at the limitation of the existing negative electrode material for sodium ions in performance, the preparation process of the negative electrode material is optimized, and the microsphere structure containing more micropore channels is formed by the preparation of the negative electrode material through the synergistic effect of N-methylmorpholine-N-oxide aqueous solution on biomass treatment combined with a hydrothermal self-assembly process, so that the processability of the negative electrode material is improved, the first coulomb efficiency of a battery is improved, and the multiplying power and the cycle performance of an electric core are improved.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
the first aspect of the present invention provides a method for preparing a negative electrode material, comprising the steps of:
s1, uniformly mixing biomass and an N-methylmorpholine-N-oxide aqueous solution in an inert atmosphere, heating to 80-150 ℃, and then preserving heat to obtain a biomass reaction solution;
s2, heating the biomass reaction liquid to 350-450 ℃, preserving heat under 1.5-3 MPa, filtering, and drying to obtain hydrothermal precursor microspheres;
and S3, carbonizing the hydrothermal precursor microsphere at 600-800 ℃ in an inert atmosphere to obtain the anode material.
Compared with the prior art, the anode material provided by the invention has the advantages that firstly, the biomass is treated by using the N-methylmorpholine-N-oxide aqueous solution at a specific temperature, so that the biomass can be rapidly swelled and partially dissolved, the consistency of the hydrothermal reaction degree of different substances in the biomass can be ensured, and a good precursor is provided for further hydrothermal reaction so as to promote the formation of microsphere structures in the anode material; further, the biomass reaction liquid is subjected to heat preservation treatment under specific pressure and temperature, so that micropore channels are formed in the swelled biomass, and the anode material is formed into a plurality of microsphere structures, and the processability of the anode material is improved; the first coulomb efficiency of the sodium ion battery can be greatly improved by applying the catalyst to the sodium ion battery; the cathode material treated by the specific process can also improve the cell multiplying power and the battery cycle performance by shortening the sodium ion migration path.
Preferably, in S1, the biomass is at least one of a fruit core, a peach shell, a rice hull, a melon seed shell, a tea seed shell, bamboo, corn stalk, coconut shell, wood dust, wheat straw, peanut shell, starch, lignin, cellulose, sucrose, or glucose.
Preferably, in S1, the particle size of the biomass is 100 μm to 300 μm.
Preferably, in the S1, the mass concentration of the N-methylmorpholine-N-oxide aqueous solution is 50% -80%.
Preferably, the consistency of the hydrothermal reaction degree of different substances in biomass can be ensured by limiting the concentration of the N-methylmorpholine-N-oxide in the N-methylmorpholine-N-oxide aqueous solution, a good precursor is provided for the hydrothermal reaction, and if the concentration of the N-methylmorpholine-N-oxide is too low, the swelling of the biomass can not reach the condition of the precursor, thereby influencing the electrochemical performance of the anode material.
Preferably, in S1, the mass ratio of the biomass to the N-methylmorpholine-N-oxide aqueous solution is (0.1-0.5): 1.
The optimized mass ratio is favorable for further improving the electrochemical performance of the electrode material, so that the first coulombic efficiency of the battery is improved, and the multiplying power and the cycle performance of the battery core are improved.
Preferably, in S1, the temperature is raised by adopting temperature programming, and the temperature raising speed is 10 ℃/min-20 ℃ min.
Preferably, in the step S1, the heat preservation time is 90-110 min.
The preferable heat preservation time can enable biomass to be swelled into a good precursor, is favorable for further promoting the anode material to form microsphere morphology and have more micropore channels, improves the first coulomb efficiency of the battery, and improves the multiplying power of the battery core and the cycle performance of the battery.
Preferably, in S1, the inert atmosphere is at least one of nitrogen, argon or helium.
Preferably, in S2, the temperature is raised by adopting temperature programming, and the temperature raising rate is 20 ℃/min-40 ℃/min.
Preferably, in the step S2, the heat preservation time is 40-60 h.
The optimal heat preservation time is favorable for enabling the anode material to reach the optimal spheroidization morphology and form more micropore channels, so that the first coulomb efficiency of the battery is improved, and the multiplying power of the battery core and the cycle performance of the battery are improved.
In the preferred embodiment, in the step S2, the drying temperature is 50-150 ℃, and the drying time is 0.5-12 h.
Preferably, in the step S3, the temperature is raised to 600-800 ℃ by adopting a temperature programming mode, and the temperature raising rate is 6-10 ℃ per minute.
Preferably, in S3, the carbonization time is 18h to 24h.
Preferably, in S3, the inert atmosphere is at least one of nitrogen, argon or helium.
The second aspect of the invention provides a negative electrode material prepared by the preparation method of the negative electrode material.
A third aspect of the present invention provides the use of the above negative electrode material in a sodium ion battery.
Compared with the prior art, the invention has the following effects:
(1) The hydrothermal precursor microsphere prepared by combining the two-step process synergism of hydrothermal treatment through soaking by using an organic solvent has the advantages of simplicity in operation, sphericization, microporation and the like, and further, the pore size and the number of the pore canal of the anode material and the spheroidization degree and the particle size of a product can be controlled by controlling the concentration of the organic solvent, the treatment temperature and the time and the temperature and the time of the hydrothermal treatment, so that the anode material with a specific micropore structure and the particle size of the microsphere is obtained, and has excellent chemical properties;
(2) The invention is beneficial to the formation of the micropore structure and the preparation of the sphericized intermediate by utilizing the synergistic effect of the two steps of technology of organic solvent soaking and hydrothermal treatment;
(3) According to the invention, the organic solvent is used for soaking and combining with the hydrothermal treatment to realize the synergistic effect, wherein the prepared micropores form micropore channels under the specific pressure, temperature and treatment time during the hydrothermal treatment, so that the migration path of sodium ions is shortened, and the cell multiplying power and the cycle performance of the battery are improved;
(4) The biomass is treated by using a specific organic solvent, so that the problem that spheroidization cannot be realized due to the difference of the hydrothermal reaction temperatures of cellulose, hemicellulose, lignin and other substances in the biomass can be avoided, the consistency of the hydrothermal reaction degrees of different substances in the biomass is ensured, and a good precursor is provided for further hydrothermal reaction so as to promote the formation of microsphere structures in the anode material; compared with a simple hydrothermal reaction, the product consistency is higher, the preparation time is shorter, and the method is suitable for industrial production;
(5) The anode material prepared by the method has high morphology roundness by selecting the organic solvent to soak and combining the two steps of reaction synergism of hydrothermal treatment and further controlling the reaction conditions, improves the controllability of the material, greatly improves the first coulomb efficiency of the battery when being applied to the battery, and improves the multiplying power of the battery core and the cycle performance of the battery by shortening the migration path of sodium ions;
(6) The cathode material prepared by the invention has low raw material cost, is renewable and is environment-friendly;
(7) The preparation method of the negative electrode material provided by the invention has the advantages of simple use equipment and process flow, easiness in operation and easiness in industrial production.
Drawings
Fig. 1 is an SEM image of the negative electrode material prepared in example 1 of the present invention.
Detailed Description
The present invention will be described in further detail with reference to the following examples and drawings in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
Example 1
The present embodiment provides a negative electrode material, including the steps of:
s1, under the condition of nitrogen, uniformly mixing biomass and an N-methylmorpholine-N-oxide aqueous solution with the mass concentration of 50%, heating to 100 ℃ at the heating rate of 10 ℃/min, and preserving heat for 100min to obtain a biomass reaction solution; wherein the biomass is a mixture of cornstalks and peanut shells with the particle size of 100-300 mu m, and the mass ratio of the biomass to the N-methylmorpholine-N-oxide aqueous solution is 0.5:1;
s2, heating the biomass reaction liquid to 400 ℃ at a heating rate of 20 ℃/min, preserving heat for 50 hours under 1.5MPa, filtering, and drying for 10 hours under 50 ℃ to obtain the hydrothermal precursor microsphere;
and S3, heating the hydrothermal precursor microsphere to 600 ℃ at a heating rate of 6 ℃/min under the condition of nitrogen, and carbonizing for 18 hours to obtain the anode material.
Example 2
The present embodiment provides a negative electrode material, including the steps of:
s1, under the argon condition, uniformly mixing biomass and an N-methylmorpholine-N-oxide aqueous solution with the mass concentration of 80%, heating to 80 ℃ at the heating rate of 20 ℃/min, and preserving heat for 90min to obtain a biomass reaction solution; wherein the biomass is a mixture of coconut shells and wood chips with the particle size of 100-300 mu m, and the mass ratio of the biomass to the N-methylmorpholine-N-oxide aqueous solution is 0.1:1;
s2, heating the biomass reaction liquid to 450 ℃ at a heating rate of 40 ℃/min, preserving heat for 40 hours under 3MPa, filtering, and drying at 100 ℃ for 12 hours to obtain the hydrothermal precursor microspheres;
and S3, heating the hydrothermal precursor microsphere to 800 ℃ at a heating rate of 10 ℃/min under the condition of argon, and carbonizing for 24 hours to obtain the anode material.
Example 3
The present embodiment provides a negative electrode material, including the steps of:
s1, under the argon condition, uniformly mixing biomass and an N-methylmorpholine-N-oxide aqueous solution with the mass concentration of 70%, heating to 150 ℃ at the heating rate of 15 ℃/min, and preserving heat for 110min to obtain a biomass reaction solution; wherein the biomass is a mixture of rice hulls and melon seed shells with the particle size of 100-300 mu m, and the mass ratio of the biomass to the N-methylmorpholine-N-oxide aqueous solution is 0.3:1;
s2, heating the biomass reaction liquid to 350 ℃ at a heating rate of 30 ℃/min, preserving heat for 60 hours under 2MPa, filtering, and drying for 5 hours at 150 ℃ to obtain the hydrothermal precursor microspheres;
and S3, heating the hydrothermal precursor microsphere to 700 ℃ at a heating rate of 7 ℃/min under the condition of argon, and carbonizing for 20 hours to obtain the anode material.
Example 4
The present embodiment provides a negative electrode material, including the steps of:
s1, under the condition of nitrogen, uniformly mixing biomass and an N-methylmorpholine-N-oxide aqueous solution with the mass concentration of 30%, heating to 100 ℃ at the heating rate of 10 ℃/min, and preserving heat for 100min to obtain a biomass reaction solution; wherein the biomass is a mixture of cornstalks and peanut shells with the particle size of 100-300 mu m, and the mass ratio of the biomass to the N-methylmorpholine-N-oxide aqueous solution is 0.5:1;
s2, heating the biomass reaction liquid to 400 ℃ at a heating rate of 20 ℃/min, preserving heat for 50 hours under 1.5MPa, filtering, and drying for 10 hours under 50 ℃ to obtain the hydrothermal precursor microsphere;
and S3, heating the hydrothermal precursor microsphere to 600 ℃ at a heating rate of 6 ℃/min under the condition of nitrogen, and carbonizing for 18 hours to obtain the anode material.
Comparative example 1
This comparative example provides a negative electrode material comprising the steps of:
in the S1, under the condition of nitrogen, uniformly mixing biomass and N-methylmorpholine-N-oxide aqueous solution with the mass concentration of 50%, heating to 200 ℃ at the heating rate of 10 ℃/min, and preserving heat for 100min to obtain biomass reaction liquid; wherein the biomass is a mixture of cornstalks and peanut shells with the particle size of 100-300 mu m, and the mass ratio of the biomass to the N-methylmorpholine-N-oxide aqueous solution is 0.5:1;
s2, heating the biomass reaction liquid to 400 ℃ at a heating rate of 20 ℃/min, preserving heat for 50 hours under 1.5MPa, filtering, and drying for 10 hours under 50 ℃ to obtain the hydrothermal precursor microsphere;
and S3, heating the hydrothermal precursor microsphere to 600 ℃ at a heating rate of 6 ℃/min under the condition of nitrogen, and carbonizing for 18 hours to obtain the anode material.
Comparative example 2
This comparative example provides a negative electrode material comprising the steps of:
s1, under the condition of nitrogen, uniformly mixing biomass and an N-methylmorpholine-N-oxide aqueous solution with the mass concentration of 50%, heating to 100 ℃ at the heating rate of 10 ℃/min, and preserving heat for 100min to obtain a biomass reaction solution; wherein the biomass is a mixture of cornstalks and peanut shells with the particle size of 100-300 mu m, and the mass ratio of the biomass to the N-methylmorpholine-N-oxide aqueous solution is 0.5:1;
s2, heating the biomass reaction liquid to 500 ℃ at a heating rate of 20 ℃/min, preserving heat for 50 hours under 1.5MPa, filtering, and drying for 10 hours under 50 ℃ to obtain the hydrothermal precursor microsphere;
and S3, heating the hydrothermal precursor microsphere to 600 ℃ at a heating rate of 6 ℃/min under the condition of nitrogen, and carbonizing for 18 hours to obtain the anode material.
Comparative example 3
This comparative example provides a negative electrode material comprising the steps of:
s1, under the condition of nitrogen, uniformly mixing biomass and an N-methylmorpholine-N-oxide aqueous solution with the mass concentration of 50%, heating to 100 ℃ at the heating rate of 10 ℃/min, and preserving heat for 100min to obtain a biomass reaction solution; wherein the biomass is a mixture of cornstalks and peanut shells with the particle size of 100-300 mu m, and the mass ratio of the biomass to the N-methylmorpholine-N-oxide aqueous solution is 0.5:1;
s2, heating the biomass reaction liquid to 400 ℃ at a heating rate of 20 ℃/min, preserving heat for 50 hours under 5MPa, filtering, and drying for 10 hours under 50 ℃ to obtain the hydrothermal precursor microsphere;
and S3, heating the hydrothermal precursor microsphere to 600 ℃ at a heating rate of 6 ℃/min under the condition of nitrogen, and carbonizing for 18 hours to obtain the anode material.
Comparative example 4
This comparative example provides a negative electrode material comprising the steps of:
s1, under the condition of nitrogen, uniformly mixing biomass and an N-methylmorpholine-N-oxide aqueous solution with the mass concentration of 50%, heating to 100 ℃ at the heating rate of 10 ℃/min, and preserving heat for 100min to obtain a biomass reaction solution; wherein the biomass is a mixture of cornstalks and peanut shells with the particle size of 100-300 mu m, and the mass ratio of the biomass to the N-methylmorpholine-N-oxide aqueous solution is 0.5:1;
s2, heating the biomass reaction liquid to 400 ℃ at a heating rate of 20 ℃/min, preserving heat for 50 hours under 1MPa, filtering, and drying for 10 hours under 50 ℃ to obtain the hydrothermal precursor microsphere;
and S3, heating the hydrothermal precursor microsphere to 600 ℃ at a heating rate of 6 ℃/min under the condition of nitrogen, and carbonizing for 18 hours to obtain the anode material.
Mixing the anode materials provided in examples 1-4 and comparative examples 1-4 with an aqueous binder (styrene-butadiene rubber SBR) and a conductive agent (carbon black SP) respectively in a mass ratio of 90:7:3, coating the mixture on a copper foil, then drying the copper foil at 90-110 ℃, and rolling and drying the copper foil to obtain a raw sheet serving as an anode sheet, wherein the coating density of the mixture of the anode materials, the aqueous binder and the conductive agent is 10mg/cm 2 Compact density 1.3g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the A metal sodium sheet was selected as a counter electrode, a membrane was a 13 μm thick PE material, a porosity of about 43%, an electrolyte was Ethylene Carbonate (EC) +propylene carbonate (PC) =1:1, and Fluoroacetate (FEC) and 1.0mol·l were added in an amount of 5% by mass of the total -1 NaClO 4 Assembling a button cell model CR2032 to obtain a sodium ion battery, and detecting gram capacity, first coulombic efficiency, battery core multiplying power and cycle performance of the sodium ion battery;
the method for detecting gram capacity and first coulombic efficiency comprises the following steps:
recording the discharge capacity and the charge capacity in the process, and calculating the mass of the active substance on the pole piece, so as to calculate the charge-discharge specific capacity of the pole piece, wherein the unit is mAh/g, and the charge capacity is divided by the discharge capacity to obtain the first charge-discharge efficiency;
m active material= (m pole piece-m copper foil) ×active material%
Discharge gram capacity = cfischarge/m active substance
Charge gram capacity = ccharge/m active substance
First discharge efficiency = charge gram capacity/discharge gram capacity x 100%;
the detection method of the battery cell multiplying power is as follows:
recording the discharge capacity and charge capacity of the process;
3C retention = step15 charge capacity/step 11 charge capacity;
the method for detecting the cycle performance comprises the following steps:
recording the discharge capacity and charge capacity of the process;
cycle retention = 500 th week step11 charge capacity/1 st week step11 charge capacity;
the specific detection results are shown in Table 1:
TABLE 1
The negative electrode material prepared by the preparation method has excellent electrochemical performance when being applied to the battery, can obviously improve the first coulombic efficiency of the battery and improve the multiplying power and the cycle performance of the battery.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, or alternatives falling within the spirit and principles of the invention.
Claims (10)
1. The preparation method of the anode material is characterized by comprising the following steps:
s1, uniformly mixing biomass and an N-methylmorpholine-N-oxide aqueous solution in an inert atmosphere, heating to 80-150 ℃, and then preserving heat to obtain a biomass reaction solution;
s2, heating the biomass reaction liquid to 350-450 ℃, preserving heat under 1.5-3 MPa, filtering, and drying to obtain hydrothermal precursor microspheres;
and S3, carbonizing the hydrothermal precursor microsphere at 600-800 ℃ in an inert atmosphere to obtain the anode material.
2. The method for producing a negative electrode material according to claim 1, wherein in S1, the particle size of the biomass is 100 μm to 300 μm.
3. The method for producing a negative electrode material according to claim 1, wherein in S1, the mass concentration of the N-methylmorpholine-N-oxide aqueous solution is 50% to 80%.
4. The method for producing a negative electrode material according to claim 1, wherein in S1, the mass ratio of the biomass to the aqueous solution of N-methylmorpholine-N-oxide is (0.1 to 0.5): 1; and/or
In the S1, the temperature is raised by adopting a programmed temperature, and the temperature raising speed is 10 ℃/min to 20 ℃ min; and/or
In the step S1, the heat preservation time is 90-110 min.
5. The method for preparing a negative electrode material according to claim 1, wherein in S2, the temperature is raised by a programmed temperature, and the temperature raising rate is 20 ℃/min to 40 ℃/min.
6. The method for preparing a negative electrode material according to claim 1, wherein in S2, the time for heat preservation is 40h to 60h.
7. The method for preparing a negative electrode material according to claim 1, wherein in S3, the temperature is raised to 600 ℃ to 800 ℃ by adopting a temperature programming mode, and the temperature raising rate is 6 ℃/min to 10 ℃/min.
8. The method for preparing a negative electrode material according to claim 1, wherein in S3, the carbonization time is 18h to 24h.
9. A negative electrode material characterized by being prepared by the preparation method of the negative electrode material according to any one of claims 1 to 8.
10. The use of the negative electrode material according to claim 9 in a sodium ion battery.
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