CN116177520A - High-performance hard carbon negative electrode material for low-temperature sodium ion battery and preparation method thereof - Google Patents
High-performance hard carbon negative electrode material for low-temperature sodium ion battery and preparation method thereof Download PDFInfo
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- 229910021385 hard carbon Inorganic materials 0.000 title claims abstract description 59
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000007773 negative electrode material Substances 0.000 title claims description 27
- 238000005406 washing Methods 0.000 claims abstract description 41
- 239000000843 powder Substances 0.000 claims abstract description 33
- 238000010438 heat treatment Methods 0.000 claims abstract description 28
- 239000002243 precursor Substances 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000003756 stirring Methods 0.000 claims abstract description 20
- 239000012535 impurity Substances 0.000 claims abstract description 19
- 238000001035 drying Methods 0.000 claims abstract description 18
- 239000010405 anode material Substances 0.000 claims abstract description 16
- 238000001816 cooling Methods 0.000 claims abstract description 16
- 238000001354 calcination Methods 0.000 claims abstract description 13
- 230000003647 oxidation Effects 0.000 claims abstract description 13
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 13
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 11
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 11
- 239000008367 deionised water Substances 0.000 claims abstract description 11
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 11
- 238000001914 filtration Methods 0.000 claims abstract description 11
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 11
- 235000017166 Bambusa arundinacea Nutrition 0.000 claims abstract description 10
- 235000017491 Bambusa tulda Nutrition 0.000 claims abstract description 10
- 241001330002 Bambuseae Species 0.000 claims abstract description 10
- 235000015334 Phyllostachys viridis Nutrition 0.000 claims abstract description 10
- 239000011425 bamboo Substances 0.000 claims abstract description 10
- 238000005554 pickling Methods 0.000 claims abstract description 10
- 230000001681 protective effect Effects 0.000 claims abstract description 10
- 238000003763 carbonization Methods 0.000 claims abstract description 9
- 238000000227 grinding Methods 0.000 claims abstract description 9
- 230000007935 neutral effect Effects 0.000 claims abstract description 6
- 239000003518 caustics Substances 0.000 claims abstract description 3
- 238000009210 therapy by ultrasound Methods 0.000 claims description 17
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 239000003513 alkali Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 229910052786 argon Inorganic materials 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 244000302661 Phyllostachys pubescens Species 0.000 claims description 6
- 235000003570 Phyllostachys pubescens Nutrition 0.000 claims description 6
- 241000959403 Pleioblastus amarus Species 0.000 claims description 2
- PWKWDCOTNGQLID-UHFFFAOYSA-N [N].[Ar] Chemical compound [N].[Ar] PWKWDCOTNGQLID-UHFFFAOYSA-N 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 230000000630 rising effect Effects 0.000 claims description 2
- 241000691155 Pteris multifida Species 0.000 claims 1
- 239000010406 cathode material Substances 0.000 abstract description 4
- 229910052573 porcelain Inorganic materials 0.000 description 20
- 239000000203 mixture Substances 0.000 description 15
- 239000001768 carboxy methyl cellulose Substances 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- 239000011734 sodium Substances 0.000 description 7
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 5
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 5
- 239000013543 active substance Substances 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- 239000006256 anode slurry Substances 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 238000010000 carbonizing Methods 0.000 description 5
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 5
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- 239000011888 foil Substances 0.000 description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 5
- 239000004570 mortar (masonry) Substances 0.000 description 5
- 230000001590 oxidative effect Effects 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 230000020477 pH reduction Effects 0.000 description 5
- 238000007781 pre-processing Methods 0.000 description 5
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 5
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 5
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical group [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 description 5
- 229910001488 sodium perchlorate Inorganic materials 0.000 description 5
- 159000000000 sodium salts Chemical class 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 4
- 239000003575 carbonaceous material Substances 0.000 description 4
- 125000004430 oxygen atom Chemical group O* 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 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
- 239000002253 acid Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000003487 electrochemical reaction Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 241000737257 Pteris <genus> Species 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
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- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
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- 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
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- 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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Abstract
The invention belongs to the technical field of hard carbon cathode materials, and discloses a preparation method of a high-performance hard carbon cathode material for a low-temperature sodium ion battery, which comprises the following steps of S1, ultrasonically treating bamboo with ethanol and deionized water, removing surface impurities, and drying to obtain a precursor sample; s2, heating the precursor sample to a pre-oxidation temperature under air for treatment, naturally cooling, grinding and crushing to obtain pre-oxidation powder; s3, pickling the pre-oxidized powder with a nitric acid solution, stirring, and filtering and washing to be neutral; then, caustic washing is carried out by potassium hydroxide solution, stirring is carried out again, filtering and washing are carried out until the solution is neutral, and pre-oxidized powder is obtained after drying; s4, heating the dried pre-oxidized powder to a carbonization temperature under a protective atmosphere for calcining, and naturally cooling to obtain the required hard carbon anode material; the invention solves the problems of low initial coulomb efficiency, low specific capacity and poor stability of cycle performance of the sodium ion battery in the low-temperature environment in the prior art, and is suitable for preparing hard carbon cathode materials.
Description
Technical Field
The invention relates to the technical field of hard carbon negative electrode materials, in particular to a high-performance hard carbon negative electrode material for a low-temperature sodium ion battery and a preparation method thereof.
Background
With the gradual maturation of lithium ion battery technology and the explosive growth of demand, the consumption of lithium resources is continuously increasing, so that the price of raw materials of lithium is rapidly increased, and the search for new alternative energy sources is particularly important. Sodium has physicochemical properties similar to those of lithium, is abundant in reserves and low in cost, and thus sodium ion batteries are receiving increasing attention as important energy storage devices for the next generation. In recent years, research on the application of hard carbon materials as negative electrode materials in sodium ion batteries has been increasing, and the hard carbon materials are considered as the negative electrode materials of sodium ion batteries most likely to realize industrial application.
The existing sodium ion battery can obtain good cycle stability and multiplying power performance at room temperature, but with the increasing strictness of large-scale energy storage requirements, the requirements on battery performance are also more strict, and the sodium ion battery needs to be capable of working in a low-temperature environment. However, the electrochemical reaction of the sodium ion battery is slow at low temperature, so that the initial coulomb efficiency, the specific capacity and the stability of the cycle performance of the sodium ion battery are low in the low-temperature environment.
Disclosure of Invention
The invention aims to provide a high-performance hard carbon negative electrode material for a low-temperature sodium ion battery and a preparation method thereof, so as to solve the problems of low initial coulomb efficiency, low specific capacity and poor stability of cycle performance of the sodium ion battery in the low-temperature environment caused by slow electrochemical reaction of the sodium ion battery in the prior art.
In order to achieve the above object, the present invention provides the following technical solutions:
the preparation method of the high-performance hard carbon negative electrode material for the low-temperature sodium ion battery comprises the following steps:
s1, pretreating bamboo, performing ultrasonic treatment with ethanol and deionized water, removing surface impurities, and drying to obtain a precursor sample;
s2, heating the precursor sample obtained in the step S1 to a pre-oxidation temperature in the air for treatment, naturally cooling, grinding and crushing to obtain pre-oxidation powder;
s3, pickling the pre-oxidized powder obtained in the step S2 with a nitric acid solution, uniformly stirring, filtering and washing, and washing with water to be neutral; then, caustic washing is carried out by potassium hydroxide solution, stirring is carried out again, filtering washing is carried out, washing is carried out until the solution is neutral, and pre-oxidized powder is obtained after drying;
and S4, heating the dried pre-oxidized powder obtained in the step S3 to a carbonization temperature under a protective atmosphere for calcining, and naturally cooling to obtain the required hard carbon anode material.
Further, in S1, the bamboo comprises one or more of Phyllostachys Pubescens, pleioblastus amarus, and Pteris multifidae; ultrasonic treatment with ethanol for not less than 30min, washing away part of impurities, ultrasonic treatment with deionized water for more than 30min, and removing obvious impurities; and the drying is to dry the washed bamboo in an oven at 80-120 ℃.
Further, in S2, the temperature of the pre-oxidation treatment is 200-300 ℃, the pre-oxidation time is 6-10 h, and the temperature rising rate is 3-5 ℃/min.
Further, in S3, the concentration of the nitric acid solution used for pickling is 0.5-3 mol/L, and the stirring time is 6-12 h; the concentration of the potassium hydroxide solution used for alkali washing is 0.5-3 mol/L; the stirring time is 6-12 h.
Further, in S4, the carbonization treatment temperature is 1200-1600 ℃, the carbonization time is 2-3 h, the heating rate is 3-5 ℃/min, and the adopted protective atmosphere is one or more inert gases selected from nitrogen, argon and nitrogen-argon.
The principle of the technical scheme is as follows:
pretreating bamboo raw materials, sequentially performing pre-oxidation and grinding and crushing to obtain pre-oxidized powder, respectively performing acid washing and alkali washing by using a nitric acid solution and a potassium hydroxide solution, and finally performing carbonization treatment to obtain a high-performance hard carbon anode material for a low-temperature sodium ion battery; the pretreatment comprises the steps of using ethanol and deionized water to carry out ultrasonic treatment to remove obvious impurities on the surface; on one hand, oxygen atoms are introduced to provide abundant active sites, and on the other hand, graphitization formation of hard carbon is promoted, and structural stability is enhanced; acid washing and alkali washing are used for removing residual impurity ions on biomass raw materials on one hand and activating on the other hand, so that the formation of a porous fiber structure is ensured.
The beneficial effects of this technical scheme:
1. the bamboo is used as the raw material for preparing the hard carbon cathode material, so that the method has the advantages of abundant resources, regeneration, wide sources and good economic benefit;
2. the selected preparation method is simple and convenient to operate, saves energy consumption, and is suitable for large-scale industrial production;
3. the obtained hard carbon anode material has large specific surface area and rich porous fiber structure, is beneficial to improving the sodium intercalation and deintercalation capacity in the circulation process and is beneficial to improving the performance of the sodium ion battery at low temperature;
4. can meet the low-temperature performance requirement of the negative electrode material of the sodium ion battery and has wide application prospect.
The high-performance hard carbon negative electrode material prepared by the preparation method of the high-performance hard carbon negative electrode material for the low-temperature sodium ion battery.
Drawings
FIG. 1 is an SEM image of a hard carbon anode material prepared in example 2 of the present invention;
fig. 2 is a first charge-discharge diagram of a hard carbon negative electrode material assembled sodium ion battery prepared in example 2 of the present invention;
FIG. 3 is a graph showing the low-temperature cycle performance of a sodium ion battery assembled from a hard carbon negative electrode material prepared in example 2 of the present invention;
Detailed Description
The invention is described in further detail below with reference to the attached drawings and embodiments:
example 1
The preparation method of the high-performance hard carbon negative electrode material for the low-temperature sodium ion battery comprises the following steps:
s1, preprocessing a precursor, namely adding ethanol into moso bamboo firstly for ultrasonic treatment for more than 30min, washing away part of impurities, and then carrying out ultrasonic treatment with deionized water for more than 30min to remove obvious impurities; after washing, transferring to an oven at 80 ℃ for drying for 12 hours to obtain a dried precursor;
s2, pre-oxidizing a precursor: putting the precursor obtained in the step S1 into a porcelain boat, then putting the porcelain boat into a muffle furnace, heating to 200 ℃ at a heating rate of 5 ℃/min, preserving heat and calcining for 8 hours, naturally cooling to obtain a pre-oxidized product, taking out, and grinding by using a mortar to obtain pre-oxidized powder;
s3, acidification and alkalization: 2g of the pre-oxidized powder obtained in the step S2 is added into the prepared 1mol/L nitric acid solution for pickling, and the mixture is placed under a magnetic stirrer for stirring for 8 hours at normal temperature, filtered and washed; transferring to a prepared 1mol/L potassium hydroxide solution for alkali washing, placing the solution in a magnetic stirrer, stirring for 8 hours at normal temperature, filtering and washing; finally transferring the mixture to an oven at 80 ℃ for drying for 12 hours to obtain dried pre-oxidized powder;
s4, carbonizing: and (3) putting 1g of the pre-oxidized powder obtained in the step (S3) into a porcelain boat, then putting the porcelain boat into a tube furnace, heating to 1400 ℃ at a heating rate of 5 ℃/min under the protection of nitrogen, preserving heat and calcining for 2 hours, and naturally cooling to obtain the high-performance hard carbon negative electrode material for the low-temperature sodium ion battery.
The prepared high-performance hard carbon anode material for the low-temperature sodium ion battery is taken as an anode active substance, uniformly mixed with sodium carboxymethylcellulose (CMC) and conductive carbon black according to the mass ratio of 8:1:1, added with a water solvent to prepare anode slurry, coated on an aluminum foil, dried for 12 hours at 100 ℃ in a vacuum drying oven, rolled and punched to obtain the hard carbon anode piece.
And (3) adopting a Na piece as a counter electrode, and assembling the obtained hard carbon negative electrode piece into a 2032 button battery in a glove box with an argon protective atmosphere of which the water and oxygen contents are less than 0.1 ppm. The sodium salt in the electrolyte is NaClO4, the concentration is 1mol/L, and the nonaqueous solvent is a mixture of EC and DEC in a volume ratio of 1:1. The test shows that the initial circle coulomb efficiency is 82%, and the cycle can be 50 circles under the current density of 500mA/g at the temperature of minus 20 ℃.
Example 2
The preparation method of the high-performance hard carbon negative electrode material for the low-temperature sodium ion battery comprises the following steps:
s1, preprocessing a precursor: adding ethanol into Phyllostachys Pubescens, performing ultrasonic treatment for more than 30min, washing away part of impurities, and performing ultrasonic treatment with deionized water for more than 30min to remove obvious impurities; after washing, transferring to an oven at 80 ℃ for drying for 12 hours to obtain a dried precursor;
s2, pre-oxidizing a precursor: putting the precursor obtained in the step S1 into a porcelain boat, then putting the porcelain boat into a muffle furnace, heating to 250 ℃ at a heating rate of 5 ℃/min, preserving heat and calcining for 8 hours, naturally cooling to obtain a pre-oxidized product, taking out, and grinding by using a mortar to obtain pre-oxidized powder;
s3, acidification and alkalization: 2g of the pre-oxidized powder obtained in the step S2 is added into the prepared 1mol/L nitric acid solution for pickling, and the mixture is placed under a magnetic stirrer for stirring for 8 hours at normal temperature, filtered and washed; transferring to a prepared 1mol/L potassium hydroxide solution for alkali washing, placing the solution in a magnetic stirrer, stirring for 8 hours at normal temperature, filtering and washing; finally transferring the mixture to an oven at 80 ℃ for drying for 12 hours to obtain dried pre-oxidized powder;
s4, carbonizing: and (3) putting 1g of the pre-oxidized powder obtained in the step (S3) into a porcelain boat, then putting the porcelain boat into a tube furnace, heating to 1400 ℃ at a heating rate of 5 ℃/min under the protection of nitrogen, preserving heat and calcining for 2 hours, and naturally cooling to obtain the high-performance hard carbon negative electrode material for the low-temperature sodium ion battery.
The prepared high-performance hard carbon anode material for the low-temperature sodium ion battery is taken as an anode active substance, uniformly mixed with sodium carboxymethylcellulose (CMC) and conductive carbon black according to the mass ratio of 8:1:1, added with a water solvent to prepare anode slurry, coated on an aluminum foil, dried for 12 hours at 100 ℃ in a vacuum drying oven, rolled and punched to obtain the hard carbon anode piece.
And (3) adopting a Na piece as a counter electrode, and assembling the obtained hard carbon negative electrode piece into a 2032 button battery in a glove box with an argon protective atmosphere of which the water and oxygen contents are less than 0.1 ppm. The sodium salt in the electrolyte is NaClO4, the concentration is 1mol/L, and the nonaqueous solvent is a mixture of EC and DEC in a volume ratio of 1:1.
As shown in figures 1 to 3, the fibrous hard carbon material prepared by testing has a first-circle coulomb efficiency as high as 88%, and can stably circulate for 200 circles at a low temperature of-20 ℃ and a current density of 500 mA/g.
Example 3
A high-performance hard carbon negative electrode material for a low-temperature sodium ion battery is prepared by the following steps:
s1, preprocessing a precursor: adding ethanol into bitter bamboo, performing ultrasonic treatment for more than 30min, washing away part of impurities, and performing ultrasonic treatment with deionized water for more than 30min to remove obvious impurities; after washing, transferring to an oven at 80 ℃ for drying for 12 hours to obtain a dried precursor;
s2, pre-oxidizing a precursor: putting the precursor obtained in the step S1 into a porcelain boat, then putting the porcelain boat into a muffle furnace, heating to 300 ℃ at a heating rate of 5 ℃/min, preserving heat and calcining for 8 hours, naturally cooling to obtain a pre-oxidized product, taking out, and grinding by using a mortar to obtain pre-oxidized powder;
s3, acidification and alkalization: 2g of the pre-oxidized powder obtained in the step S2 is added into the prepared 1mol/L nitric acid solution for pickling, and the mixture is placed under a magnetic stirrer for stirring for 8 hours at normal temperature, filtered and washed; transferring to a prepared 1mol/L potassium hydroxide solution for alkali washing, placing the solution in a magnetic stirrer, stirring for 8 hours at normal temperature, filtering and washing; finally transferring the mixture to an oven at 80 ℃ for drying for 12 hours to obtain dried pre-oxidized powder;
s4, carbonizing: and (3) putting 1g of the pre-oxidized powder obtained in the step (S3) into a porcelain boat, then putting the porcelain boat into a tube furnace, heating to 1400 ℃ at a heating rate of 5 ℃/min under the protection of nitrogen, preserving heat and calcining for 2 hours, and naturally cooling to obtain the high-performance hard carbon negative electrode material for the low-temperature sodium ion battery.
The prepared high-performance hard carbon anode material for the low-temperature sodium ion battery is taken as an anode active substance, uniformly mixed with sodium carboxymethylcellulose (CMC) and conductive carbon black according to the mass ratio of 8:1:1, added with a water solvent to prepare anode slurry, coated on an aluminum foil, dried for 12 hours at 100 ℃ in a vacuum drying oven, rolled and punched to obtain the hard carbon anode piece.
And (3) adopting a Na piece as a counter electrode, and assembling the obtained hard carbon negative electrode piece into a 2032 button battery in a glove box with an argon protective atmosphere of which the water and oxygen contents are less than 0.1 ppm. The sodium salt in the electrolyte is NaClO4, the concentration is 1mol/L, and the nonaqueous solvent is a mixture of EC and DEC in a volume ratio of 1:1. The test shows that the initial coulomb efficiency is 84%, and the cycle can be 100 circles under the current density of 500mA/g at the temperature of 20 ℃ below zero.
Comparative example 1
A high-performance hard carbon negative electrode material for a low-temperature sodium ion battery is prepared by the following steps:
s1, preprocessing a precursor: adding ethanol into Phyllostachys Pubescens, performing ultrasonic treatment for more than 30min, washing away part of impurities, and performing ultrasonic treatment with deionized water for more than 30min to remove obvious impurities; after washing, transferring to an oven at 80 ℃ for drying for 12 hours to obtain a dried precursor;
s2, pre-oxidizing a precursor: putting the precursor obtained in the step S1 into a porcelain boat, then putting the porcelain boat into a muffle furnace, heating to 250 ℃ at a heating rate of 5 ℃/min, preserving heat and calcining for 8 hours, naturally cooling to obtain a pre-oxidized product, taking out, and grinding by using a mortar to obtain pre-oxidized powder;
s3, acidification and alkalization: 2g of the pre-oxidized powder obtained in the step S2 is added into the prepared 1mol/L nitric acid solution for pickling, and the mixture is placed under a magnetic stirrer for stirring for 8 hours at normal temperature, filtered and washed; transferring to a prepared 1mol/L potassium hydroxide solution for alkali washing, placing the solution in a magnetic stirrer, stirring for 8 hours at normal temperature, filtering and washing; finally transferring the mixture to an oven at 80 ℃ for drying for 12 hours to obtain dried pre-oxidized powder;
s4, carbonizing: and (3) putting 1g of the pre-oxidized powder obtained in the step (S3) into a porcelain boat, then putting the porcelain boat into a tube furnace, heating to 1200 ℃ at a heating rate of 5 ℃/min under the protection of nitrogen, preserving heat and calcining for 2 hours, and naturally cooling to obtain the high-performance hard carbon negative electrode material for the low-temperature sodium ion battery.
The prepared high-performance hard carbon anode material for the low-temperature sodium ion battery is taken as an anode active substance, uniformly mixed with sodium carboxymethylcellulose (CMC) and conductive carbon black according to the mass ratio of 8:1:1, added with a water solvent to prepare anode slurry, coated on an aluminum foil, dried for 12 hours at 100 ℃ in a vacuum drying oven, rolled and punched to obtain the hard carbon anode piece.
And (3) adopting a Na piece as a counter electrode, and assembling the obtained hard carbon negative electrode piece into a 2032 button battery in a glove box with an argon protective atmosphere of which the water and oxygen contents are less than 0.1 ppm. The sodium salt in the electrolyte is NaClO4, the concentration is 1mol/L, and the nonaqueous solvent is a mixture of EC and DEC in a volume ratio of 1:1. The test shows that the initial circle coulomb efficiency is 80%, and the initial circle coulomb efficiency can circulate for 80 circles under the current density of 500mA/g at the temperature of minus 20 ℃.
Comparative example 2
A high-performance hard carbon negative electrode material for a low-temperature sodium ion battery is prepared by the following steps:
s1, preprocessing a precursor: adding ethanol into Phyllostachys Pubescens, performing ultrasonic treatment for more than 30min, washing away part of impurities, and performing ultrasonic treatment with deionized water for more than 30min to remove obvious impurities; after washing, transferring to an oven at 80 ℃ for drying for 12 hours to obtain a dried precursor;
s2, pre-oxidizing a precursor: putting the precursor obtained in the step S1 into a porcelain boat, then putting the porcelain boat into a muffle furnace, heating to 250 ℃ at a heating rate of 5 ℃/min, preserving heat and calcining for 8 hours, naturally cooling to obtain a pre-oxidized product, taking out, and grinding by using a mortar to obtain pre-oxidized powder;
s3, acidification and alkalization: 2g of the pre-oxidized powder obtained in the step S2 is added into the prepared 1mol/L nitric acid solution for pickling, and the mixture is placed under a magnetic stirrer for stirring for 8 hours at normal temperature, filtered and washed; transferring to a prepared 1mol/L potassium hydroxide solution for alkali washing, placing the solution in a magnetic stirrer, stirring for 8 hours at normal temperature, filtering and washing; finally transferring the mixture to an oven at 80 ℃ for drying for 12 hours to obtain dried pre-oxidized powder;
s4, carbonizing: and (3) putting 1g of the pre-oxidized powder obtained in the step (S3) into a porcelain boat, then putting the porcelain boat into a tube furnace, heating to 1600 ℃ at a heating rate of 5 ℃/min under the protection of nitrogen, preserving heat and calcining for 2 hours, and naturally cooling to obtain the high-performance hard carbon negative electrode material for the low-temperature sodium ion battery.
The prepared high-performance hard carbon anode material for the low-temperature sodium ion battery is taken as an anode active substance, uniformly mixed with sodium carboxymethylcellulose (CMC) and conductive carbon black according to the mass ratio of 8:1:1, added with a water solvent to prepare anode slurry, coated on an aluminum foil, dried for 12 hours at 100 ℃ in a vacuum drying oven, rolled and punched to obtain the hard carbon anode piece.
And (3) adopting a Na piece as a counter electrode, and assembling the obtained hard carbon negative electrode piece into a 2032 button battery in a glove box with an argon protective atmosphere of which the water and oxygen contents are less than 0.1 ppm. The sodium salt in the electrolyte is NaClO4, the concentration is 1mol/L, and the nonaqueous solvent is a mixture of EC and DEC in a volume ratio of 1:1. The test shows that the initial circle coulomb efficiency is 85%, and the initial circle coulomb efficiency can circulate for 120 circles at the temperature of-20 ℃ and the current density of 500 mA/g.
In summary, it is known that the high-performance hard carbon negative electrode material for the low-temperature sodium ion battery can be used as a battery negative electrode active material, so that the specific capacity of the battery is higher, and the battery has excellent cycle stability. The hard carbon material prepared by the method of example 2 has the optimal performance, and the size of the hard carbon open pores is suitable for oxygen atom doping due to the proper pre-oxidation temperature, and the too large or too small open pores are not beneficial to oxygen atom doping, if the too large open pores are easy to lose oxygen atoms, the too small open pores are not high in doping rate; in addition, the proper pre-oxidation temperature makes the subsequent carbonization process easier to graphitize, and provides structural stability.
The foregoing is merely exemplary embodiments of the present invention, and detailed technical solutions or features that are well known in the art have not been described in detail herein. It should be noted that, for those skilled in the art, several variations and modifications can be made without departing from the technical solution of the present invention, and these should also be regarded as the protection scope of the present invention, which does not affect the effect of the implementation of the present invention and the practical applicability of the patent. The protection scope of the present application shall be subject to the content of the claims, and the description of the specific embodiments and the like in the specification can be used for explaining the content of the claims.
Claims (6)
1. The preparation method of the high-performance hard carbon anode material for the low-temperature sodium ion battery is characterized by comprising the following steps of:
s1, pretreating bamboo, performing ultrasonic treatment with ethanol and deionized water, removing surface impurities, and drying to obtain a precursor sample;
s2, heating the precursor sample obtained in the step S1 to a pre-oxidation temperature in the air for treatment, naturally cooling, grinding and crushing to obtain pre-oxidation powder;
s3, pickling the pre-oxidized powder obtained in the step S2 with a nitric acid solution, uniformly stirring, filtering and washing, and washing with water to be neutral; then, caustic washing is carried out by potassium hydroxide solution, stirring is carried out again, filtering washing is carried out, washing is carried out until the solution is neutral, and pre-oxidized powder is obtained after drying;
and S4, heating the dried pre-oxidized powder obtained in the step S3 to a carbonization temperature under a protective atmosphere for calcining, and naturally cooling to obtain the required hard carbon anode material.
2. The method for preparing the high-performance hard carbon anode material for the low-temperature sodium ion battery according to claim 1, which is characterized in that: in S1, bamboo comprises one or more of Phyllostachys Pubescens, pleioblastus amarus and Pteris Multifida; ultrasonic treatment with ethanol for not less than 30min, washing away part of impurities, ultrasonic treatment with deionized water for more than 30min, and removing obvious impurities; and the drying is to dry the washed bamboo in an oven at 80-120 ℃.
3. The method for preparing the high-performance hard carbon anode material for the low-temperature sodium ion battery according to claim 1, which is characterized in that: in S2, the temperature of the pre-oxidation treatment is 200-300 ℃, the pre-oxidation time is 6-10 h, and the temperature rising rate is 3-5 ℃/min.
4. The method for preparing the high-performance hard carbon anode material for the low-temperature sodium ion battery according to claim 1, which is characterized in that: in S3, the concentration of the nitric acid solution used for pickling is 0.5-3 mol/L, and the stirring time is 6-12 h; the concentration of the potassium hydroxide solution used for alkali washing is 0.5-3 mol/L; the stirring time is 6-12 h.
5. The method for preparing the high-performance hard carbon anode material for the low-temperature sodium ion battery according to claim 1, which is characterized in that: in S4, the carbonization treatment temperature is 1200-1600 ℃, the carbonization time is 2-3 h, the heating rate is 3-5 ℃/min, and the adopted protective atmosphere is one or more inert gases of nitrogen, argon and nitrogen-argon.
6. A high-performance hard carbon negative electrode material prepared by the method for preparing a high-performance hard carbon negative electrode material for a low-temperature sodium ion battery according to any one of claims 1 to 5.
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