CN116692828A - Sodium ion battery and preparation and application of bamboo-based composite hard carbon negative electrode active material thereof - Google Patents
Sodium ion battery and preparation and application of bamboo-based composite hard carbon negative electrode active material thereof Download PDFInfo
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- 235000017166 Bambusa arundinacea Nutrition 0.000 title claims abstract description 89
- 235000017491 Bambusa tulda Nutrition 0.000 title claims abstract description 89
- 241001330002 Bambuseae Species 0.000 title claims abstract description 89
- 235000015334 Phyllostachys viridis Nutrition 0.000 title claims abstract description 89
- 239000011425 bamboo Substances 0.000 title claims abstract description 89
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 58
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 229910021385 hard carbon Inorganic materials 0.000 title claims abstract description 37
- 239000002131 composite material Substances 0.000 title claims abstract description 28
- 239000007773 negative electrode material Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 31
- 239000000843 powder Substances 0.000 claims abstract description 25
- 239000003513 alkali Substances 0.000 claims abstract description 20
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- 239000008107 starch Substances 0.000 claims abstract description 19
- 235000019698 starch Nutrition 0.000 claims abstract description 19
- 238000010306 acid treatment Methods 0.000 claims abstract description 17
- 238000003763 carbonization Methods 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000006183 anode active material Substances 0.000 claims abstract description 10
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- 239000002253 acid Substances 0.000 claims description 26
- 239000000463 material Substances 0.000 claims description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 13
- 239000000243 solution Substances 0.000 claims description 13
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- 238000009656 pre-carbonization Methods 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
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- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 claims description 8
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- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 4
- 239000012670 alkaline solution Substances 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 4
- 238000010000 carbonizing Methods 0.000 claims description 4
- 239000000174 gluconic acid Substances 0.000 claims description 4
- 235000012208 gluconic acid Nutrition 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 239000002388 carbon-based active material Substances 0.000 claims description 3
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- 238000005406 washing Methods 0.000 claims description 3
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- 229910000288 alkali metal carbonate Inorganic materials 0.000 claims description 2
- 150000008041 alkali metal carbonates Chemical class 0.000 claims description 2
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- 239000010405 anode material Substances 0.000 abstract description 4
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- 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 12
- 238000002474 experimental method Methods 0.000 description 12
- 229910052708 sodium Inorganic materials 0.000 description 12
- 239000011734 sodium Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 10
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
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- 229910001416 lithium ion Inorganic materials 0.000 description 7
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
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- 230000002195 synergetic effect Effects 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 230000006399 behavior Effects 0.000 description 3
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- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
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- 239000007788 liquid Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 1
- XNCSCQSQSGDGES-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]propyl-(carboxymethyl)amino]acetic acid Chemical compound OC(=O)CN(CC(O)=O)C(C)CN(CC(O)=O)CC(O)=O XNCSCQSQSGDGES-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 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
- 150000007513 acids Chemical class 0.000 description 1
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- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
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- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
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- 229910052751 metal Inorganic materials 0.000 description 1
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- 229910001092 metal group alloy Inorganic materials 0.000 description 1
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- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 235000010413 sodium alginate Nutrition 0.000 description 1
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- 238000001179 sorption measurement Methods 0.000 description 1
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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
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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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 sodium ion batteries, and particularly relates to a preparation method of a bamboo-based composite hard carbon negative electrode active material of a sodium ion battery, wherein bamboo powder is subjected to alkali treatment in advance and then acid treatment to prepare pretreated bamboo powder; and dispersing the pretreated bamboo powder and starch in an alcohol-water solution for heat treatment, and then performing crosslinking and carbonization treatment to obtain the bamboo-based composite hard carbon anode active material. The invention also comprises the anode material prepared by the method and the application of the anode material in sodium ion batteries. The method can prepare the hard carbon anode material with sodium ion adaptation, and is beneficial to improving the electrochemical performance of a sodium ion battery.
Description
Technical Field
The invention belongs to the technical field of sodium ion batteries, and particularly relates to the field of hard carbon negative electrode materials of sodium ion batteries.
Background
The transformation of the energy structure to non-fossil energy under the double-carbon target is accelerated, the increase of the renewable energy duty ratio becomes a deterministic trend, and the new energy storage demand bursts out. In order to meet the carbon neutralization requirement and realize the cleanness and low carbonization of the energy structure, the country is also actively going out of the energy storage support policy, and the energy storage construction is forced, so that the support is provided for the energy storage development of the country. In various novel energy storage technologies, a lithium ion battery takes an absolute predominance, and the lithium ion battery energy storage has great advantages in the aspects of cycle times, energy density, response speed and the like. However, due to the scarcity and uneven regional distribution of lithium resources, the cost of lithium ion batteries is continuously increased, the further large-scale application of the lithium ion batteries is limited, and the sodium ion batteries are expected to accelerate permeation in electric energy storage by virtue of the advantages of the sodium ion batteries.
The sodium resource reserves are rich (the sodium content in the crust reaches 2.75 percent and is higher than the lithium content by 0.065 per mill), the distribution is uniform, the cost is low, the sustainable performance is strong, the application prospect is wide, and the method has important strategic significance for reducing the external dependence of lithium resources in China. However, the atomic radius of sodium ions is large compared with that of lithium ions, and the thermodynamic properties of the formed interlayer compound are unstable, and conventional materials suitable for intercalation and deintercalation of lithium ions are difficult to meet the requirements of efficient intercalation and deintercalation of sodium ions as well, which is one of the main reasons why lithium ion batteries have been widely commercialized, while sodium ion batteries similar to the theoretical ones remain in the laboratory stage.
Therefore, if commercialization of the sodium ion battery is to be achieved, it is important to select an appropriate negative electrode material. Compared with metal alloys and metal oxides having fatal defects such as high volume expansion rate and low conductivity, hard carbon is the industrial grade negative electrode with the most development prospect of sodium ion batteries. Among them, widely available, biomass with unique microstructure for sodium storage is a popular application. However, the hard carbon materials prepared from different biomass materials have large structural difference and uneven sodium storage performance; moreover, the existing biomass hard carbon preparation process is complex and unstable in performance, so that development of a biomass hard carbon material which is easy to prepare, excellent in performance and stable is urgently needed.
Disclosure of Invention
Aiming at the problems of unsatisfactory suitability of biomass carbon to sodium ions, unsatisfactory performances such as sodium storage capacity, multiplying power and the like, the invention provides a preparation method of a bamboo-based composite hard carbon negative electrode active material of a sodium ion battery, and aims to prepare the hard carbon negative electrode active material with excellent performances such as capacity, multiplying power and the like, which is suitable for the sodium ion battery.
The second aim of the invention is to provide the bamboo-based composite anode hard carbon active material prepared by the preparation method.
The third object of the invention is to provide the application of the bamboo-based composite hard carbon negative electrode active material in sodium ion batteries.
The fourth object of the present invention is to provide a sodium ion battery comprising the bamboo-based composite hard carbon negative electrode active material.
Different biomasses have different material compositions and microstructure characteristics, and the schemes and effects of preparing electrode materials are different. Therefore, the invention tries to prepare the anode material suitable for the sodium ion battery by adopting the bamboo as the raw material. However, it is found that when bamboo is used for preparing the sodium-electricity adaptive material, various technical problems caused by bamboo raw materials need to be faced, for example: first, the bamboo carbonization process has more gas micromolecules discharged, which is easy to cause the formation of open pores and the increase of specific surface area, promotes the excessive decomposition of electrolyte to form a thicker SEI film, and inhibits the diffusion and migration of sodium ions. Second, the inherently high defect content at the edges or layers of short-range disordered carbon layers tends to also cause irreversible sodium ion adsorption, resulting in poor specific capacity and first-turn coulombic efficiency. Third,: because of the structural characteristics of the bamboo fiber, a pore canal and a path which are suitable for embedding and taking off sodium ions are difficult to form; fourth,: the bamboo contains a large amount of microelements, wherein the microelements contain electrochemical beneficial components, and the electrochemical beneficial components are not too much, so that how to selectively utilize the beneficial components and reduce the interference of the beneficial components as much as possible is another main problem affecting the preparation effect. Fifth, biomass carbonized materials such as bamboo often show morphology features of disordered fragmentation, and the compacted density of pole pieces is low, which is not beneficial to the future uniform industrial production.
Aiming at the problems faced by preparing the sodium ion-adaptive anode active material from the bamboo raw materials, the invention provides the following solutions:
a preparation method of a bamboo-based composite hard carbon anode active material of a sodium ion battery comprises the following steps:
step (1):
pre-treating bamboo powder with alkali, and then treating with acid to obtain pretreated bamboo powder;
step (2):
and (3) dispersing the pretreated bamboo powder and starch in an alcohol-water solution for heat treatment, and then carbonizing to obtain the bamboo-based composite hard carbon anode active material.
Aiming at the problem that the bamboo base is difficult to adapt to the application requirement of a sodium ion battery due to the physical and chemical characteristics of the bamboo base, the invention innovatively carries out alkali-before-acid pretreatment, then pre-carbonization, alcohol-water solvothermal treatment with starch and carbonization treatment, so that the electrochemical beneficial components in the bamboo raw material can be selectively utilized, the microstructure and the surface activity of the bamboo raw material are improved, the application requirement of the sodium ion battery is met, the embedding and de-embedding behaviors of the sodium ion battery are improved, the transmission network and the transmission path are optimized, and the performances of the hard carbon cathode capacity, the coulombic efficiency, the multiplying power and the like of the sodium ion battery are further improved.
According to the invention, the bamboo is used as a raw material, and the cooperation of the following processes is realized, so that the problem of sodium ion battery discomfort caused by physical and chemical characteristics of the bamboo raw material can be solved, and the capacity, coulomb efficiency, multiplying power and other performances of the bamboo in sodium electricity can be improved synergistically.
In the invention, the bamboo powder is bamboo stem powder;
preferably, the bamboo stems are dried and then crushed to obtain the bamboo powder; the particle size is, for example, 10 to 30. Mu.m.
Aiming at the problems faced by preparing the negative electrode of the sodium ion battery from the bamboo raw material, the invention innovatively adopts the pretreatment process of firstly carrying out alkali and then carrying out acid, can solve the problem of selectively utilizing the components, and is beneficial to improving the performance of the prepared material in sodium electricity.
In the invention, the alkaline solute in the alkaline solution adopted in the alkaline treatment stage comprises at least one of alkali metal hydroxide, alkali metal carbonate and ammonia water;
preferably, the alkaline solute is NaOH.
Preferably, the concentration of alkaline solute in the alkaline solution is 0.1 to 1.5M, more preferably 0.9 to 1.1M;
the invention researches find that the temperature of the alkali treatment stage is preferably controlled, so that the combined synergistic effect of the alkali treatment stage and the subsequent process is further improved. Preferably, the temperature of the alkaline treatment stage is from 20 to 100 ℃, more preferably from 50 to 90 ℃, still more preferably from 60 to 80 ℃, most preferably from 75 to 85 ℃.
In the present invention, the time for the alkali treatment is 5 to 10 hours, and is more preferably 7 to 9 hours in view of the treatment cost and efficiency.
In the invention, the acid solution adopted in the acid treatment stage has at least one of HCl, sulfuric acid, nitric acid, citric acid, EDTA and gluconic acid as the acidic solute. It was found that the use of HCl, compared to other single acids, surprisingly further improved the suitability of the bamboo-based material and sodium ions, contributing to a further synergistic improvement of the properties of the resulting material.
Further preferably, the acidic solute comprises a combined acid of HCl and an auxiliary acid, and the auxiliary acid is at least one of citric acid, EDTA and gluconic acid. The molar ratio of HCl to auxiliary acid is, for example, 0.5-1.5:1. According to the research of the invention, the preferred components are helpful for further selectively regulating and controlling beneficial components in the bamboo raw material, and are beneficial for controlling the sodium ion adaptation physical and chemical structure of the bamboo raw material, so that the prepared material has better electrochemical performance.
Preferably, the concentration of the acidic solute in the acid solution is 0.5 to 3M, and may further preferably be 0.7 to 1.2M in view of the treatment cost;
in the present invention, the acid treatment stage may be carried out at room temperature, for example, at a temperature of 10 to 40 ℃.
In the invention, the acid treatment time is 8-15H, and the treatment efficiency can be further 10-14H;
in the invention, after the acid treatment, water washing treatment is carried out, for example, the filtrate is washed until the filtrate is neutral.
In the invention, the pretreated material is pre-carbonized, and compared with the pre-carbonized material which is treated by alkali and then acid, the method is favorable for solving the problem of the unadapted preparation of the sodium-electricity negative electrode caused by the raw material components of the bamboo.
In the invention, the atmosphere in the pre-carbonization stage is a protective atmosphere; for example, at least one of nitrogen and argon may be used.
In the present invention, the temperature of the pre-carbonization is not particularly required, and may be 500 to 700 ℃, for example;
in the present invention, the pre-carbonization time can be adjusted as needed, for example, when the temperature is high, the treatment time can be shortened, when the temperature is relatively low, the treatment time can be prolonged, and further, the treatment efficiency can be 1 to 3 hours.
In the invention, starch is innovatively adopted to repair the pre-carbonized pore structure and surface, and the combined control of alcohol-water solvent and heat treatment conditions is further matched, so that the structure repair effect can be further improved, and the electrochemical performance of the prepared material in sodium electricity can be further improved.
Preferably, the weight ratio of the material and the starch of the bamboo powder after pre-carbonization is 1-10: 1, further can be 2-4:1; preferably in proportions, the performance can be further synergistically improved.
Preferably, the alcohol aqueous solution is a mixed solution of C1-C4 alcohol and water;
preferably, in the alcohol aqueous solution, the volume percentage of alcohol is 80-90V%;
preferably, the volume ratio of the total weight of the pre-carbonized material and the starch to the aqueous alcohol solution is 30-80mL/g;
preferably, the temperature of the heat treatment is 60 to 80 ℃.
The time of the heat treatment is not particularly limited, and may be, for example, 1 to 8 hours, and further may be 3 to 5 hours.
In the invention, carbonization comprises a first-stage carbonization process at a temperature of T1 and a second-stage carbonization process at a temperature of T2;
preferably, the temperature of T1 is 400-600 ℃, and further can be 450-550 ℃;
preferably the temperature of T2 is 1000-1600 ℃, further can be 1200-1400 ℃;
preferably, the heat preservation time T1 at the temperature T1 is 1-3 h;
preferably, the holding time T2 at the temperature T2 is 1 to 3 hours.
The invention also provides the bamboo-based composite hard carbon anode active material prepared by the preparation method.
The preparation method can endow the prepared material with special physical and chemical characteristics, and the material with the characteristics can unexpectedly show excellent sodium ion adaptation effect and can show better electrochemical performance in sodium electricity.
The invention also provides application of the bamboo-based composite hard carbon anode active material prepared by the preparation method, and the bamboo-based composite hard carbon anode active material is used as an anode active material for preparing sodium ion batteries.
In the present invention, the negative electrode active material may be prepared into a desired sodium ion battery and parts thereof based on known processes and apparatuses. For example, the negative electrode active material and the binder can be compounded and coated on a current collector to be used as a negative electrode plate for a sodium ion battery.
The invention also provides a sodium ion button half battery which comprises a hard carbon material pole piece serving as a positive electrode, a glass fiber diaphragm and a sodium negative electrode which are sequentially compounded, and is characterized in that the positive electrode piece is the bamboo-based composite hard carbon negative electrode active material prepared by the preparation method.
A sodium ion battery (full battery) comprises a negative electrode, a diaphragm and a positive electrode which are sequentially compounded, wherein the negative electrode comprises the bamboo-based composite hard carbon negative electrode active material prepared by the preparation method.
In the present invention, other materials and structures may be known in the industry, except that the negative electrode contains the bamboo-based composite hard carbon negative electrode active material.
The invention has the advantages that:
aiming at the problem that the bamboo base is difficult to adapt to the application requirement of the sodium ion battery due to the physical and chemical characteristics of the bamboo base, the invention innovatively pre-carries out alkali-before-acid pretreatment, then pre-carbonizes, and carries out alcohol-water solvothermal treatment and carbonization treatment on starch, so that the electrochemical beneficial components in the bamboo raw material can be selectively utilized, the microstructure and the surface activity of the bamboo raw material are improved, the bamboo raw material is adapted to the application requirement of the sodium ion battery, the transmission network and the transmission path are improved, the embedding and de-embedding behaviors of the sodium ion battery are optimized, and the performances such as the capacity, the coulombic efficiency and the multiplying power of the sodium ion battery are further improved. The invention is further favorable for further synergistically improving the performance of the prepared material by optimizing the conditions such as alkali treatment, acid treatment, material compounding and the like.
Drawings
Fig. 1 is an SEM image of the negative active material prepared in example 1;
FIG. 2 is a test chart of example 1;
Detailed Description
For a further understanding of the present invention, the present invention is illustrated below in conjunction with the following examples for further explanation of the features and advantages of the present invention, but the present invention is not limited to the following examples.
In the present invention, the bamboo used refers to the bamboo stem portion unless specifically stated otherwise. The particle size of the bamboo powder formed by conventional crushing treatment is not particularly required, and the D50 particle size of the bamboo powder is 10-30um in the following cases except for the special statement.
In the following cases, the room temperature refers to a temperature of between 20 and 35℃unless specifically stated otherwise.
Example 1
Step (1): bamboo powder preparation
Bamboo is selected as a precursor, residual moisture is removed in a baking oven at 100 ℃, and the bamboo is coarsely crushed into particles (bamboo powder) by using a jaw crusher.
Step (2): pretreatment of
Adding alkali liquor (1M NaOH solution with the liquid-solid ratio of 20 mL/g) into the dried crushed bamboo material (bamboo powder) in the step (1), treating for 8 hours at 80 ℃, centrifuging, and then treating with acid liquor (1M hydrochloric acid with the liquid-solid ratio of 20 mL/g) for 12 hours (the temperature in the acid treatment stage is room temperature); finally, washing the mixture by pure water until the filtrate is neutral, and drying the mixture in an oven at 80 ℃ to obtain a pretreated material;
step (3): starch repair
Pre-carbonizing the pre-treated material for 2 hours at the temperature of 600 ℃ under nitrogen to obtain a pre-carbonized material, and then mixing the pre-carbonized material with the following components in percentage by weight: 3 and starch, dispersing in 80% ethanol water solution (liquid-solid ratio is 80 mL/g), and heat preserving at 70 ℃ for 4h, and then evaporating and drying to obtain precursor;
step (4): two-stage carbonization
Carbonizing the precursor in nitrogen atmosphere at 500deg.C (marked as T1) for 2 hr (marked as T1), ball milling in planetary ball mill at 400rpm for 30min, and sieving to obtain particle diameter D 50 20um powder was finally transferred to a vacuum tube furnace and carbonized at 1300 c (labeled T2) for 2h (labeled T2) with a temperature ramp rate of 5 c/min for the T1/T2 stage. The negative electrode active material is prepared.
And uniformly mixing the hard carbon composite material obtained in the example 1 and sodium alginate according to the mass ratio of 9:1, mixing and grinding the mixture with a solvent N-methylpyrrolidone (NMP), coating the mixture on a copper foil current collector, and carrying out vacuum drying at 80 ℃ to obtain the negative electrode plate. The battery assembly and test were: stamping the cathode plate into an electrode plate with the diameter of 10mm, taking metal sodium as a counter electrode and glass fiber as a diaphragm, wherein the electrolyte is 1M NaPF 6 EC DEC (1:1), assembled into CR2032 button cell in glove box. Constant current charge and discharge tests were carried out at 25℃at a current density of 30 mA/g. The electrochemical performance test results were as follows: the specific capacity of the first discharge is 368mAh/g, and the first-circle coulomb efficiency is 90.96%. The reversible capacity is 248mAh/g after 100 circles of 1C circulation.
Example 2
The only difference compared to example 1 is that the conditions of the alkali treatment of step 2 are changed, the experimental groups are respectively:
group A: the temperature of the alkaline treatment stage was 60 ℃. Other process parameters, experimental procedures were consistent with example 1. Electrochemical performance test results: the specific capacity of the first discharge is 363mAh/g, and the first-circle coulomb efficiency is 90.08%. The reversible capacity is 239mAh/g after 100 circles of 1C circulation.
Group B: 100 ℃ of the alkali treatment stage. Other process parameters, experimental procedures were consistent with example 1. Electrochemical performance test results: the specific capacity of the first discharge is 331mAh/g, and the first-circle coulomb efficiency is 83.78%. The reversible capacity is 232mAh/g after 100 circles of 1C circulation.
Group C: the temperature of the alkali treatment stage is room temperature (20-25 ℃). Other process parameters, experimental procedures were consistent with example 1. Electrochemical performance test results: the specific capacity of the first discharge is 344mAh/g, and the first-circle coulomb efficiency is 88.78%. The reversible capacity is 229mAh/g after 100 circles of 1C circulation.
Example 3
The only difference compared to example 1 is that the conditions of the acid treatment are changed, the experimental groups are:
group A: the acid liquid is nitric acid. Other process parameters, experimental procedures were consistent with example 1. Electrochemical performance test results: the specific capacity of the first discharge is 347mAh/g, and the first-circle coulomb efficiency is 89.09%. The cycle was 100 turns at 1C, and the reversible capacity was 233mAh/g.
Group B: the acid liquid is sulfuric acid. Other process parameters, experimental procedures were consistent with example 1. Electrochemical performance test results: the specific capacity of the first discharge is 352mAh/g, and the first-circle coulomb efficiency is 90.27%. The reversible capacity is 238mAh/g after 100 circles of 1C circulation.
Group C: the acid solution is a mixed acid of 0.5M hydrochloric acid and 0.5 MEDTA. Other process parameters, experimental procedures were consistent with example 1. Electrochemical performance test results: the specific capacity of the first discharge is 375mAh/g, and the first-circle coulomb efficiency is 91.87%. The reversible capacity is 251mAh/g after 100 circles of 1C circulation.
It is evident from examples 1 and 3 that the use of HCl in combination with other processes synergistically improves the performance and that the combination of HCl with an auxiliary acid innovatively allows for an unexpected further improvement of the synergistic effect.
Example 4
The only difference compared to example 1 is that the conditions of step 3 are changed, the experimental groups are:
group A: the mass ratio of the pre-carbonized material to the starch is 5:5. other process parameters, experimental procedures were consistent with example 1. Electrochemical performance test results: the specific capacity of the first discharge is 364mAh/g, and the first-circle coulomb efficiency is 87.73%. The reversible capacity is 227mAh/g after 100 circles of 1C circulation.
Group B: the mass ratio of the pre-carbonized material to the starch is 9:1. other process parameters, experimental procedures were consistent with example 1. Electrochemical performance test results: the specific capacity of the first discharge is 352mAh/g, and the first-circle coulomb efficiency is 88.97%. The reversible capacity is 239mAh/g after 100 circles of 1C circulation.
Group C: the ethanol volume of the ethanol aqueous solution was changed to 90%. Other process parameters, experimental procedures were consistent with example 1. Electrochemical performance test results: the specific capacity of the first discharge is 352mAh/g, and the first-circle coulomb efficiency is 89.71%. The reversible capacity is 237mAh/g after 100 circles of 1C circulation.
Group D: the temperature of the pre-carbonization was 500 ℃. Other process parameters, experimental procedures were consistent with example 1. Electrochemical performance test results: the specific capacity of the first discharge is 356mAh/g, and the first-circle coulomb efficiency is 88.53%. The reversible capacity is 241mAh/g after 100 circles of 1C circulation.
It is evident from examples 1 and 4A, 4B that a better synergistic effect is obtained with a preferred pre-carbonisation material to starch of 2-4:1.
Example 5
The only difference compared to example 1 is that the conditions of step 4 are changed, in particular;
group A: t1 is 400 ℃, and T1 is 3h; t2 is 1100℃and T2 is 3h. Other process parameters, experimental procedures were consistent with example 1. Electrochemical performance test results: the specific capacity of the first discharge is 361mAh/g, and the first-circle coulomb efficiency is 87.28%. The reversible capacity is 238mAh/g after 100 circles of 1C circulation.
Group B: t1 is 600 ℃, and T1 is 1h; t2 is 1500 ℃, T2 is 1.5h: other process parameters, experimental procedures were consistent with example 1. Electrochemical performance test results: the specific capacity of the first discharge is 349mAh/g, and the first-circle coulomb efficiency is 89.17%. The reversible capacity is 227mAh/g after 100 circles of 1C circulation.
Comparative example 1
The difference compared to example 1 is that the bamboo is replaced with an equal amount of cotton, and other operations and parameters are the same as in example 1. The electrochemical performance test results were: the specific capacity of the first discharge is 322mAh/g, and the first-circle coulomb efficiency is 85.17%. The reversible capacity is 202mAh/g after 100 circles of 1C circulation.
Comparative example 2
The difference from example 1 is that the bamboo powder of step 1 was directly subjected to step 3 and the subsequent steps without performing the treatment of step 2, and other parameters were the same as those of example 1. The electrochemical performance test results were: the specific capacity of the first discharge is 289mAh/g, and the first-circle coulomb efficiency is 79.37%. The reversible capacity is 186mAh/g after 100 circles of 1C circulation.
Comparative example 3
The difference from example 1 is that in step 2, only the alkali treatment is performed, the acid treatment is not performed, and the conditions of the alkali treatment are the same as example 1. The electrochemical performance test results were: the specific capacity of the first discharge is 314mAh/g, and the first-circle coulomb efficiency is 82.17%. The reversible capacity is 208mAh/g after 100 circles of 1C circulation.
Comparative example 4
The difference from example 1 is that in step 2, only the acid treatment is performed, the alkali treatment is not performed, and the conditions of the acid treatment are the same as example 1. The electrochemical performance test results were: the specific capacity of the first discharge is 309mAh/g, and the first-circle coulomb efficiency is 84.17%. The reversible capacity is 198mAh/g after 100 circles of 1C circulation.
Comparative example 5
The difference compared with example 1 is only that in step 2, the acid treatment is performed in advance, followed by the alkali treatment, and the parameter conditions of the acid treatment and the alkali treatment are the same as those of example 1. The electrochemical performance test results were: the specific capacity of the first discharge is 349mAh/g, and the first-circle coulomb efficiency is 86.93%. The reversible capacity is 227mAh/g after 100 circles of 1C circulation.
Example 1 and comparative example 5 demonstrate that the process of the present invention can unexpectedly solve the problem of the mismatch between the bamboo and sodium ion batteries and can unexpectedly achieve better electrochemical performance.
Comparative example 6
The only difference compared to example 1 is that the starch is replaced with glucose of equal weight, the other operations and parameters are the same as in example 1. The electrochemical performance test results were: the specific capacity of the first discharge is 338mAh/g, and the first-circle coulomb efficiency is 86.27%. The reversible capacity is 216mAh/g after 100 circles of 1C circulation.
Comparative example 7
The only difference compared to example 1 is that the starch is replaced with an equal weight of bitumen, the other operations and parameters being the same as in example 1. The electrochemical performance test results were: the specific capacity of the first discharge is 302mAh/g, and the first-circle coulomb efficiency is 84.66%. The reversible capacity is 223mAh/g after 100 circles of 1C circulation.
Comparative example 8
The difference compared with example 1 is only that in step 3, the aqueous ethanol solution is replaced with pure water, and the amount of pure water and the amount of aqueous ethanol solvent are the same. The electrochemical performance test results were: the specific capacity of the first discharge is 342mAh/g, and the first-circle coulomb efficiency is 86.94%. The reversible capacity is 211mAh/g after 100 circles of 1C circulation.
Comparative example 9
The difference compared with example 1 is only that in step 3, the pre-carbonized material and starch are ball milled dry for 30min at a rotational speed of 300r/min. The electrochemical performance test results were: the specific capacity of the first discharge is 329mAh/g, and the first-circle coulomb efficiency is 83.07%. The reversible capacity is 203mAh/g after 100 circles of 1C circulation.
In summary, aiming at the problem that the application requirement of the sodium ion battery is difficult to adapt due to the physical and chemical characteristics of the bamboo base, the invention innovatively pre-carries out alkali-before-acid pretreatment, then pre-carbonizes, and carries out alcohol-water solvothermal treatment and carbonization treatment on starch, so that the electrochemical beneficial components in the bamboo raw material can be selectively utilized, the microstructure and the surface activity of the bamboo raw material can be improved, the bamboo raw material can adapt to the application requirement of the sodium ion battery, the transmission network and the transmission path can be improved, the embedding and the de-embedding behaviors of the sodium ion battery can be optimized, and the capacity, coulombic efficiency, multiplying power and other performances of the sodium ion battery can be further improved. The invention is further favorable for further synergistically improving the performance of the prepared material by optimizing the conditions such as alkali treatment, acid treatment, material compounding and the like.
The foregoing is merely a preferred example of the present invention, and it should be appreciated that the present invention is not limited to the embodiments of the present invention, and that those skilled in the art can make corresponding variations or modifications according to the main concept of the present invention, so that the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (10)
1. The preparation method of the bamboo-based composite negative hard carbon active material of the sodium ion battery is characterized by comprising the following steps:
step (1):
pre-treating bamboo powder with alkali, and then treating with acid to obtain pretreated bamboo powder;
step (2):
and (3) dispersing the pretreated bamboo powder and starch in an alcohol-water solution for heat treatment, and then carbonizing to obtain the bamboo-based composite hard carbon anode active material.
2. The method for preparing a bamboo-based composite hard carbon negative electrode active material of a sodium ion battery according to claim 1, wherein the bamboo powder is bamboo stem powder;
preferably, the bamboo stems are dried and then crushed to obtain the bamboo powder;
preferably, the particle size of the bamboo powder is 10-30um.
3. The method for preparing a bamboo-based composite hard carbon negative electrode active material of a sodium ion battery according to claim 1, wherein the alkaline solute used in the alkaline solution in the alkaline treatment stage comprises at least one of alkali metal hydroxide, alkali metal carbonate and ammonia water;
preferably, the alkaline solute is NaOH;
preferably, the concentration of the alkaline solute in the alkaline solution is 0.1-1.5M;
preferably, the temperature of the alkaline treatment stage is from 20 to 100 ℃, more preferably from 50 to 90 ℃, still more preferably from 60 to 80 ℃, most preferably from 75 to 85 ℃;
preferably, the alkali treatment is carried out for a period of time of from 5 to 10 hours.
4. The method for preparing a bamboo-based composite hard carbon negative electrode active material of a sodium ion battery according to claim 1, wherein the acid solution used in the acid treatment stage is at least one of HCl, sulfuric acid, nitric acid, citric acid, EDTA and gluconic acid; further preferably, the acidic solute comprises a combined acid of HCl and an auxiliary acid, and the auxiliary acid is at least one of citric acid, EDTA and gluconic acid; preferably, the molar ratio of HCl to auxiliary acid is, for example, 0.5 to 1.5:1;
preferably, the concentration of the acidic solute in the acid solution is 0.5-3M;
preferably, the acid treatment time is 8-15 hours;
preferably, after the acid treatment, a water washing treatment is performed until neutral.
5. The method for preparing a bamboo-based composite hard carbon negative electrode active material of a sodium ion battery according to claim 1, wherein the atmosphere in the pre-carbonization stage is a protective atmosphere;
preferably, the temperature of the pre-carbonization is 500-700 ℃;
preferably, the pre-carbonization time is 1 to 3 hours.
6. The method for preparing the bamboo-based composite hard carbon negative electrode active material of the sodium ion battery as claimed in claim 1, wherein the mass ratio of the material of the bamboo powder subjected to pre-carbonization to the starch is 1-10: 1, a step of;
preferably, the alcohol aqueous solution is a mixed solution of C1-C4 alcohol and water;
preferably, in the alcohol aqueous solution, the volume percentage of alcohol is 80-90%;
preferably, the volume ratio of the total weight of the pre-carbonized material and the starch to the aqueous alcohol solution is 30-80mL/g;
preferably, the temperature of the heat treatment is 60-80 ℃;
preferably, after the heat treatment, the subsequent carbonization treatment is performed after evaporation, desolventizing and drying.
7. The method for preparing a bamboo-based composite anode hard carbon active material of a sodium ion battery according to claim 1, wherein the carbonization comprises a first stage carbonization at a temperature of T1 and a second stage carbonization at a temperature of T2;
preferably, the temperature of T1 is 400-600 ℃;
preferably, the temperature of T2 is 1000-1600 ℃;
preferably, the heat preservation time T1 at the temperature T1 is 1-3 h;
preferably, the holding time T2 at the temperature T2 is 1 to 3 hours.
8. A bamboo-based composite hard carbon anode active material prepared by the preparation method of any one of claims 1 to 7.
9. Use of the bamboo-based composite hard carbon negative electrode active material prepared by the preparation method according to any one of claims 1 to 7 as a negative electrode active material for preparing a sodium ion battery.
10. A sodium ion battery comprising a negative electrode, a separator and a positive electrode which are sequentially compounded, wherein the negative electrode comprises the bamboo-based composite hard carbon negative electrode active material prepared by the preparation method of any one of claims 1 to 7.
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