CN116632233B - High-performance sodium ion battery doped hard carbon negative electrode material and preparation method thereof - Google Patents
High-performance sodium ion battery doped hard carbon negative electrode material and preparation method thereof Download PDFInfo
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- CN116632233B CN116632233B CN202310885225.9A CN202310885225A CN116632233B CN 116632233 B CN116632233 B CN 116632233B CN 202310885225 A CN202310885225 A CN 202310885225A CN 116632233 B CN116632233 B CN 116632233B
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- 229910021385 hard carbon Inorganic materials 0.000 title claims abstract description 41
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 31
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000007773 negative electrode material Substances 0.000 title claims description 28
- 229920005610 lignin Polymers 0.000 claims abstract description 38
- 239000010405 anode material Substances 0.000 claims abstract description 23
- 238000010438 heat treatment Methods 0.000 claims abstract description 23
- 239000000843 powder Substances 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000002156 mixing Methods 0.000 claims abstract description 17
- 238000002791 soaking Methods 0.000 claims abstract description 16
- 239000002904 solvent Substances 0.000 claims abstract description 16
- 238000010000 carbonizing Methods 0.000 claims abstract description 14
- 230000005496 eutectics Effects 0.000 claims abstract description 14
- 239000000463 material Substances 0.000 claims abstract description 14
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 13
- 239000011858 nanopowder Substances 0.000 claims abstract description 13
- 238000003763 carbonization Methods 0.000 claims abstract description 12
- 239000012298 atmosphere Substances 0.000 claims abstract description 11
- 239000000919 ceramic Substances 0.000 claims abstract description 10
- 239000012190 activator Substances 0.000 claims abstract description 6
- 230000001681 protective effect Effects 0.000 claims abstract description 6
- 230000003213 activating effect Effects 0.000 claims abstract description 5
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 5
- 150000002815 nickel Chemical class 0.000 claims abstract description 5
- 239000012266 salt solution Substances 0.000 claims abstract description 4
- 235000017166 Bambusa arundinacea Nutrition 0.000 claims description 29
- 235000017491 Bambusa tulda Nutrition 0.000 claims description 29
- 241001330002 Bambuseae Species 0.000 claims description 29
- 235000015334 Phyllostachys viridis Nutrition 0.000 claims description 29
- 239000011425 bamboo Substances 0.000 claims description 29
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 28
- KWIUHFFTVRNATP-UHFFFAOYSA-N glycine betaine Chemical compound C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 claims description 16
- 239000004310 lactic acid Substances 0.000 claims description 14
- 235000014655 lactic acid Nutrition 0.000 claims description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 229960003237 betaine Drugs 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 5
- 239000011261 inert gas Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 9
- 238000005406 washing Methods 0.000 abstract description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 7
- 230000008569 process Effects 0.000 abstract description 6
- 239000002243 precursor Substances 0.000 abstract description 5
- 239000011148 porous material Substances 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 230000002195 synergetic effect Effects 0.000 abstract description 3
- 238000001035 drying Methods 0.000 abstract description 2
- 238000005554 pickling Methods 0.000 abstract description 2
- 239000012535 impurity Substances 0.000 abstract 1
- 238000002604 ultrasonography Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 22
- 230000000052 comparative effect Effects 0.000 description 9
- 239000005539 carbonized material Substances 0.000 description 7
- 238000000227 grinding Methods 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- 238000007873 sieving Methods 0.000 description 7
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 238000003760 magnetic stirring Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 150000002816 nickel compounds Chemical class 0.000 description 6
- 229910052700 potassium Inorganic materials 0.000 description 6
- 239000011591 potassium Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000001291 vacuum drying Methods 0.000 description 6
- 238000000605 extraction Methods 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 238000009830 intercalation Methods 0.000 description 4
- 230000002687 intercalation Effects 0.000 description 4
- 239000003575 carbonaceous material Substances 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000000428 dust Substances 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
- 239000010419 fine particle Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000012982 microporous membrane Substances 0.000 description 1
- 230000000051 modifying effect Effects 0.000 description 1
- 230000002688 persistence Effects 0.000 description 1
- 150000003109 potassium Chemical class 0.000 description 1
- 150000003112 potassium compounds Chemical class 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 150000005837 radical ions Chemical class 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- -1 that is Chemical compound 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- 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
- 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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
-
- 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 relates to the technical field of sodium ion batteries, and discloses a high-performance hard carbon anode material of a doped sodium ion battery and a preparation method thereof, wherein the preparation method comprises the following steps: s1, taking precursor powder, soaking the precursor powder in a eutectic solvent, placing the eutectic solvent in an ultrasonic environment, and heating for reaction; after the reaction is finished, absolute ethyl alcohol is added, and the lignin is obtained through water washing, drying and fine crushing; s2, mixing lignin, ferroelectric ceramic, graphene nano powder and an activating agent which are prepared in the step S1, and soaking in a nickel salt solution; and (3) transferring into a mixed protective atmosphere, heating and carbonizing, and pickling to remove impurities to obtain the hard carbon anode material. According to the invention, lignin with more terminal groups and higher fluidity is extracted through the synergistic effect of ultrasound and the eutectic solvent, so that the formation of pores in the carbonization process is promoted; and in the carbonization process, the activator and the nickel salt are synergistic, so that the electrochemical performance of the material can be improved.
Description
Technical Field
The invention relates to the technical field of sodium ion batteries, in particular to a high-performance hard carbon negative electrode material of a doped sodium ion battery and a preparation method thereof.
Background
With the gradual exhaustion of fossil energy and the continuous development of energy technology, a rechargeable battery mainly comprising a lithium ion battery has excellent electrochemical performance, and is the most suitable technical means for portable energy storage at present. However, the lithium element has a small amount of resources and is unevenly distributed, which greatly limits the development of its large-scale application. Based on this, research and development on rechargeable batteries is beginning to gradually shift to other metal ion batteries.
Sodium ions are metal elements with fourth crust abundance arrangement, are rich in resources and wide in distribution, have the advantages of easy acquisition and low cost, and because sodium ions and lithium ions are similar in intercalation chemistry, the development and application of the sodium ion battery are expected to exceed those of the lithium ion battery. In the sodium ion battery, as the ion diameter of sodium ions is similar to the interplanar spacing of graphite, that is, graphite is not suitable for intercalation of sodium ions, the current negative electrode material of the sodium ion battery mainly adopts an oxide negative electrode material, an alloy negative electrode material, a sulfide negative electrode material or an organic negative electrode material. However, the negative electrode material for the sodium ion battery has the problems of poor electrochemical performance, low battery cycle efficiency, serious environmental pollution and high cost, and does not accord with the development concept of green persistence.
Therefore, how to prepare the hard carbon negative electrode material for the sodium ion battery with high performance by adopting a material which is more green and environment-friendly and has low price becomes an important problem to be solved at present.
Disclosure of Invention
The invention aims to solve the technical problems that:
currently, the existing negative electrode materials for sodium ion batteries mostly adopt oxide negative electrode materials, alloy negative electrode materials, sulfide negative electrode materials, organic negative electrode materials and the like, and have the problems of poor electrochemical performance, low battery cycle efficiency and the like, serious environmental pollution and high cost.
The invention adopts the technical scheme that:
the invention provides a high-performance sodium ion battery doped hard carbon anode material, which comprises the following steps:
s1, taking precursor powder, placing the precursor powder in an ultrasonic-eutectic system, and heating for reaction; after the reaction is finished, lignin is obtained through post-treatment;
s2, mixing the lignin, the ferroelectric ceramic, the graphene nano powder and the activating agent which are prepared in the step S1, soaking in a nickel salt solution, transferring into a mixed protective atmosphere, and heating and carbonizing to obtain the hard carbon anode material.
Preferably, the eutectic solvent comprises betaine and lactic acid in a mass ratio of 1:1-6.
Preferably, the activator is selected from KOH, znCl 2 NaOH or K 2 CO 3 One or more of the following.
Preferably, the mixed protective atmosphere comprises reducing gas and inert gas in a volume ratio of 1:4-99.
Preferably, in step S1, the solid-to-liquid ratio is controlled to be 1:10-50 when the precursor powder is immersed in the eutectic solvent.
Preferably, the temperature is controlled to be 100-180 ℃ and the reaction time is 2-8h during the heating reaction.
Preferably, during carbonization, the heating rate is controlled to be 1-10 ℃/min, the carbonization temperature is 600-1600 ℃, and the carbonization time is 2-6h.
Preferably, the ferroelectric ceramic is selected from BaTiO 3 、PbTiO 3 、Bi 4 Ti 3 O 12 Or one or more of pyrochlores.
Preferably, in the step S2, the mass ratio of lignin, ferroelectric ceramic, graphene nano powder and activating agent is 1-10:0.5-5:1-3:1.
The invention adopts the technical mechanism and has the beneficial effects that:
in the invention, the ultrasonic and eutectic solvent method are adopted to cooperate in the lignin extraction process, so that the breakage of lignin-carbohydrate bonds is promoted, the mass transfer resistance can be reduced by the mechanical acoustic effect of ultrasonic waves, the solvent medium can enter the solute more easily, the lignin with lower molecular weight is obtained, the lower molecular weight is favorable for bringing more terminal groups and higher fluidity, and the porous structure is favorable for forming in the subsequent carbonization process.
In the process of preparing the hard carbon anode material, ferroelectric ceramic and graphene nano powder are introduced, and the material is promoted to form a richer space pore structure when the material is endowed with higher dielectric constant and other properties. By H 2 The mixed gas of Ar is used as a protective atmosphere, wherein H 2 Has strong returnThe original property can reduce the generation of oxygen-containing covalent bonds and dangling bonds in the carbonization process, and reduce the content of oxygen and sulfur; and with the generation of a large amount of gas, more pore structures can be formed in the material, namely the micropore content is increased, the formation of a cross-linked structure can be reduced, and the growth of a graphite layer and Na are facilitated + Is not limited to the absorption of (a). In addition, KOH and Ni (NO 3 ） 2 Synergistic effect, ni + The existence of (2) can provide a large number of micropores for the material, increase the specific surface area of the material, and further provide Na for the material + Provides more active sites for the storage of KOH, and activation of KOH can cause more structural distortion of the material, K + The intercalation of (2) can increase the initial coulombic efficiency, and the generated pore structure can reduce the transmission resistance of ions and electrons and shorten Na + Allowing more electrolyte to enter the micropores, and improving the charge and discharge efficiency of the microporous membrane; finally through HNO 3 The solution is washed to remove the potassium/nickel compound, which is beneficial to improving the specific capacity of the battery and improving the cycle performance of the battery.
Drawings
FIG. 1 is an electron microscopic view of a hard carbon negative electrode material in example 1;
fig. 2 is a charge-discharge curve of a sodium ion battery using the hard carbon negative electrode material of example 2 to prepare a negative electrode sheet.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions of the embodiments of the present invention will be clearly and completely described below. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The invention provides a high-performance sodium ion battery doped hard carbon anode material, which comprises the following steps:
(1) Extracting lignin:
taking bamboo, crushing, dedusting, grinding and sieving the bamboo to obtain bamboo powder; mixing betaine (Bet) and Lactic Acid (LA) according to a mass ratio of 1:1-6, and placing the mixture in a magnetic stirring oil bath at 30-80 ℃ for treatment for 1-5h to obtain a transparent uniform eutectic solvent DES; soaking bamboo powder in DES, controlling solid-liquid ratio to be 1:10-50, placing in an ultrasonic cleaner, reacting for 2-8h at 100-180deg.C, adding anhydrous ethanol after reaction, and stopping reaction to obtain extractive solution; adding the extract into excessive cold water, stirring, filtering, washing, and vacuum drying to obtain lignin.
In the invention, lignin with low relative molecular weight is extracted from cheap and easily obtained biomass materials, and compared with the lignin extraction method adopted by the existing anode material, the lignin extraction method has the advantages of low requirements on extraction process conditions, higher extraction rate and product purity, better thermal stability of the extracted lignin and contribution to the formation of a porous structure in subsequent carbonization.
(2) Preparation of hard carbon negative electrode material
Mixing lignin, ferroelectric ceramic, graphene nano powder and an activating agent according to the mass ratio of 1-10:0.5-5:1-3:1, and soaking in a nickel salt solution for 8-24 hours after uniformly mixing; heating and carbonizing for 2-6h under the mixed atmosphere of reducing gas/inert gas with the volume ratio of 1:4-99, controlling the heating rate to be 1-10 ℃/min, and the carbonizing temperature to be 600-1600 ℃; and (3) placing the carbonized material in an acid solution, and pickling to remove potassium/nickel compounds to obtain the hard carbon anode material.
In the present invention, the ferroelectric ceramic is selected from BaTiO 3 、PbTiO 3 、Bi 4 Ti 3 O 12 Or one or more of pyrochlores; the activator is selected from KOH and ZnCl 2 NaOH or K 2 CO 3 One or more of the following; acid solution used for acid washing, and a compound formed by acid radical ions and metal ions in an activator are easy to dissolve in water.
< example >
Example 1
(1) Extracting lignin:
taking bamboo, crushing, dedusting, grinding and sieving the bamboo to obtain bamboo powder; mixing betaine (Bet) and Lactic Acid (LA) according to a mass ratio of 1:3, and placing the mixture in a 50 ℃ magnetic stirring oil bath kettle for 3 hours to obtain a transparent uniform eutectic solvent DES; soaking bamboo powder in DES, controlling solid-liquid ratio to be 1:20, placing in an ultrasonic cleaner, reacting for 4 hours at 150 ℃, adding absolute ethyl alcohol after the reaction, and stopping the reaction to obtain an extracting solution; adding the extract into excessive cold water, stirring, filtering, washing, and vacuum drying to obtain lignin.
(2) Preparing a hard carbon anode material:
the mass ratio is 2:2.5:1:1, lignin and BaTiO 3 Mixing graphene nano powder and KOH, and placing in Ni (NO) 3 ） 2 Soaking in (0.1-1M) solution for 24h; h in a volume ratio of 1:9 2 Heating and carbonizing for 4 hours in Ar atmosphere, controlling the heating rate to be 5 ℃/min and the carbonizing temperature to be 800 ℃; placing the carbonized material in HNO 3 And (3) removing the potassium/nickel compound from the (1-6M) solution to obtain the hard carbon anode material.
Example 2
(1) Extracting lignin:
taking bamboo, crushing, dedusting, grinding and sieving the bamboo to obtain bamboo powder; mixing betaine (Bet) and Lactic Acid (LA) according to a mass ratio of 1:3, and placing the mixture in a 50 ℃ magnetic stirring oil bath kettle for 3 hours to obtain a transparent uniform eutectic solvent DES; soaking bamboo powder in DES, controlling solid-liquid ratio to be 1:20, placing in an ultrasonic cleaner, reacting for 4 hours at 150 ℃, adding absolute ethyl alcohol after the reaction, and stopping the reaction to obtain an extracting solution; adding the extract into excessive cold water, stirring, filtering, washing, and vacuum drying to obtain lignin.
(2) Preparing a hard carbon anode material:
the mass ratio is 2:2.5:1:1 mixing lignin with pyrochlore, graphene nano powder and KOH, and placing in Ni (NO) 3 ） 2 Soaking in (0.1-1M) solution for 24h; h in a volume ratio of 1:9 2 Heating and carbonizing for 4 hours in Ar atmosphere, controlling the heating rate to be 5 ℃/min and the carbonizing temperature to be 800 ℃; placing the carbonized material in HNO 3 And (3) removing the potassium/nickel compound from the (1-6M) solution to obtain the hard carbon anode material.
Example 3
(1) Extracting lignin:
taking bamboo, crushing, dedusting, grinding and sieving the bamboo to obtain bamboo powder; mixing betaine (Bet) and Lactic Acid (LA) according to a mass ratio of 1:2, and placing the mixture in a 75 ℃ magnetic stirring oil bath kettle for 3 hours to obtain a transparent uniform eutectic solvent DES; soaking bamboo powder in DES, controlling solid-liquid ratio to be 1:30, placing in an ultrasonic cleaner, reacting for 3h at 170 ℃, adding absolute ethyl alcohol after the reaction, and stopping the reaction to obtain an extracting solution; adding the extract into excessive cold water, stirring, filtering, washing, and vacuum drying to obtain lignin.
(2) Preparing a hard carbon anode material:
the mass ratio is 2:2.5:1:1, lignin and BaTiO 3 Mixing graphene nano powder and KOH, and placing in Ni (NO) 3 ） 2 Soaking in (0.1-1M) solution for 24h; h in a volume ratio of 1:9 2 Heating and carbonizing for 2-6h in Ar atmosphere, controlling the heating rate to be 5 ℃/min, and controlling the carbonizing temperature to be 800 ℃; placing the carbonized material in HNO 3 And (3) removing the potassium/nickel compound from the (1-6M) solution to obtain the hard carbon anode material.
Example 4
(1) Extracting lignin:
taking bamboo, crushing, dedusting, grinding and sieving the bamboo to obtain bamboo powder; mixing betaine (Bet) and Lactic Acid (LA) according to a mass ratio of 1:3, and placing the mixture in a 50 ℃ magnetic stirring oil bath kettle for 3 hours to obtain a transparent uniform eutectic solvent DES; soaking bamboo powder in DES, controlling solid-liquid ratio to be 1:20, placing in an ultrasonic cleaner, reacting for 4 hours at 150 ℃, adding absolute ethyl alcohol after the reaction, and stopping the reaction to obtain an extracting solution; adding the extract into excessive cold water, stirring, filtering, washing, and vacuum drying to obtain lignin.
(2) Preparing a hard carbon anode material:
the mass ratio is 5:4:2:1, lignin and BaTiO 3 Mixing graphene nano powder and KOH, and placing in Ni (NO) 3 ） 2 Soaking in (0.1-1M) solution for 16h; h in a volume ratio of 1:90 2 Heating and carbonizing under Ar atmosphere6h, controlling the heating rate to be 2 ℃/min and the carbonization temperature to be 1200 ℃; placing the carbonized material in HNO 3 And (3) removing the potassium/nickel compound from the (1-6M) solution to obtain the hard carbon anode material.
Example 5
(1) Extracting lignin:
taking bamboo, crushing, dedusting, grinding and sieving the bamboo to obtain bamboo powder; mixing betaine (Bet) and Lactic Acid (LA) according to a mass ratio of 1:3, and placing the mixture in a 50 ℃ magnetic stirring oil bath kettle for 3 hours to obtain a transparent uniform eutectic solvent DES; soaking bamboo powder in DES, controlling solid-liquid ratio to be 1:20, placing in an ultrasonic cleaner, reacting for 4 hours at 150 ℃, adding absolute ethyl alcohol after the reaction, and stopping the reaction to obtain an extracting solution; adding the extract into excessive cold water, stirring, filtering, washing, and vacuum drying to obtain lignin.
(2) Preparing a hard carbon anode material:
the mass ratio is 10:5:1:1, lignin and BaTiO 3 Mixing graphene nano powder and KOH, and placing in Ni (NO) 3 ） 2 Soaking in (0.1-1M) solution for 24h; h in a volume ratio of 1:4 2 Heating and carbonizing for 2 hours in Ar atmosphere, controlling the heating rate to 8 ℃/min and the carbonizing temperature to 100 ℃; placing the carbonized material in HNO 3 And (3) removing the potassium/nickel compound from the (1-6M) solution to obtain the hard carbon anode material.
Comparative example
Comparative example 1
The difference between this comparative example and example 1 is that lignin is directly heated to 800 ℃ at a heating rate of 5 ℃/min and carbonized for 2 hours to obtain a hard carbon material.
Comparative example 2
The difference between this comparative example and example 1 is that when lignin is extracted, wood is taken, and bamboo powder is obtained by pulverizing, dust removing, grinding and sieving; and then dissolving the bamboo powder in deionized water, stewing, distilling and drying to obtain lignin.
Comparative example 3
This comparative example differs from example 1 in that lignin was used for preparationIn the case of hard carbon anode material, lignin is directly put in Ni (NO) 3 ） 2 (0.1-1M) solution, not mixed with BaTiO 3 Mixing graphene nano-powder and KOH.
< test example >
Sample: examples 1 to 5, comparative examples 1 to 3
Fig. 1 is an electron microscope image of a hard carbon negative electrode material of example 1, the carbonized material surface adsorbs a plurality of smaller fine particles, which has a modifying effect on the carbon material surface, and the intercalation of the potassium compound can also destroy the graphite structure of the carbon layer, thereby improving the graphitization-like degree and the charge-discharge specific capacity. As shown in fig. 2, which is a charge-discharge graph of example 2, the specific discharge capacity reaches about 370mAh/g or more under the condition of a charge-discharge flow rate of 0.1C, and the specific discharge capacity is significantly better than that of the existing sodium ion battery, which can indicate that the change of the hard carbon structure can significantly improve the electrochemical performance of the material.
Samples were withdrawn, and the specific capacity and first coulombic efficiency of the materials in each group of samples were measured to reflect the electrochemical properties and the like of the resulting materials, with the results as shown in table 1 below:
table 1 electrochemical properties of the samples
From the electrochemical performance comparisons of each set of samples in table 1 above, it can be found that: the hard carbon negative electrode material prepared by the preparation method provided by the invention, namely the samples in examples 1-5, has obviously higher specific capacity and first coulombic efficiency compared with the hard carbon material prepared by the traditional process in comparative examples 1-3. Therefore, the preparation method and the hard carbon negative electrode material of the sodium ion battery prepared by the preparation method have higher electrochemical performance, and can solve the problems of low battery cycle efficiency and poor electrochemical performance of the existing negative electrode material of the sodium ion battery.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (9)
1. The preparation method of the high-performance sodium ion doped battery hard carbon anode material is characterized by comprising the following steps of:
s1, taking bamboo powder, placing the bamboo powder in an ultrasonic-eutectic solvent, and heating for reaction; after the reaction is finished, lignin is obtained through post-treatment;
s2, mixing the lignin, the ferroelectric ceramic, the graphene nano powder and the activating agent which are prepared in the step S1, soaking in a nickel salt solution, transferring into a mixed protective atmosphere, and heating and carbonizing to obtain a hard carbon anode material;
the activator is selected from KOH, znCl 2 NaOH or K 2 CO 3 One or more of the following.
2. The method for preparing the high-performance sodium ion doped battery hard carbon anode material according to claim 1, wherein the eutectic solvent comprises betaine and lactic acid in a mass ratio of 1:1-6.
3. The method for preparing the high-performance sodium ion doped battery hard carbon anode material according to claim 1, wherein the mixed protective atmosphere comprises a reducing gas and an inert gas in a volume ratio of 1:4-99.
4. The method for preparing a hard carbon negative electrode material of a high-performance doped sodium ion battery according to claim 1, wherein in the step S1, when the bamboo powder is soaked in the eutectic solvent, the solid-liquid ratio is controlled to be 1:10-50.
5. The method for preparing the high-performance sodium ion doped battery hard carbon negative electrode material according to claim 1, wherein the temperature is controlled to be 100-180 ℃ and the reaction time is 2-8h during the heating reaction.
6. The method for preparing the high-performance sodium ion doped battery hard carbon negative electrode material according to claim 1, wherein the heating rate is controlled to be 1-10 ℃/min, the carbonization temperature is 600-1600 ℃, and the carbonization time is 2-6h during carbonization.
7. The method for producing a hard carbon negative electrode material for a high-performance sodium ion doped battery according to any one of claims 1 to 6, wherein the ferroelectric ceramic is selected from BaTiO 3 、PbTiO 3 、Bi 4 Ti 3 O 12 Or one or more of pyrochlores.
8. The method for preparing a hard carbon negative electrode material of a high-performance doped sodium ion battery according to any one of claims 1 to 6, wherein in the step S2, the mass ratio of lignin, ferroelectric ceramic, graphene nano powder and an activator is 1-10:0.5-5:1-3:1.
9. A high performance sodium ion doped battery hard carbon negative electrode material, characterized in that the material is prepared by the preparation method of any one of claims 1 to 8.
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