CN117361497A - Preparation method of sodium ion battery anode material with high first efficiency - Google Patents
Preparation method of sodium ion battery anode material with high first efficiency Download PDFInfo
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- CN117361497A CN117361497A CN202311400354.0A CN202311400354A CN117361497A CN 117361497 A CN117361497 A CN 117361497A CN 202311400354 A CN202311400354 A CN 202311400354A CN 117361497 A CN117361497 A CN 117361497A
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- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 52
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 239000010405 anode material Substances 0.000 title claims abstract description 25
- 239000007833 carbon precursor Substances 0.000 claims abstract description 81
- 238000003763 carbonization Methods 0.000 claims abstract description 71
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 70
- 229910021385 hard carbon Inorganic materials 0.000 claims abstract description 62
- 238000005087 graphitization Methods 0.000 claims abstract description 57
- 238000002156 mixing Methods 0.000 claims abstract description 46
- 239000003054 catalyst Substances 0.000 claims abstract description 41
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 40
- 229910052751 metal Inorganic materials 0.000 claims abstract description 39
- 239000002184 metal Substances 0.000 claims abstract description 39
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 38
- 238000005406 washing Methods 0.000 claims abstract description 30
- 239000002253 acid Substances 0.000 claims abstract description 27
- 150000001768 cations Chemical class 0.000 claims abstract description 27
- 239000012298 atmosphere Substances 0.000 claims abstract description 26
- 230000001681 protective effect Effects 0.000 claims abstract description 23
- 239000002243 precursor Substances 0.000 claims abstract description 21
- 230000003197 catalytic effect Effects 0.000 claims abstract description 17
- 238000010000 carbonizing Methods 0.000 claims abstract description 12
- 230000007935 neutral effect Effects 0.000 claims abstract description 10
- 238000005245 sintering Methods 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000009766 low-temperature sintering Methods 0.000 claims abstract description 8
- 239000007789 gas Substances 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 21
- 239000000843 powder Substances 0.000 claims description 20
- 230000000630 rising effect Effects 0.000 claims description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 15
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 10
- 238000000498 ball milling Methods 0.000 claims description 7
- 238000006555 catalytic reaction Methods 0.000 claims description 7
- 238000005554 pickling Methods 0.000 claims description 7
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 6
- 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 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 6
- 239000008103 glucose Substances 0.000 claims description 6
- 239000007791 liquid phase Substances 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 239000005011 phenolic resin Substances 0.000 claims description 6
- 229920001568 phenolic resin Polymers 0.000 claims description 6
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 5
- 235000019253 formic acid Nutrition 0.000 claims description 5
- 238000003801 milling Methods 0.000 claims description 5
- 235000006408 oxalic acid Nutrition 0.000 claims description 5
- 239000004576 sand Substances 0.000 claims description 5
- 235000009496 Juglans regia Nutrition 0.000 claims description 4
- 229920002472 Starch Polymers 0.000 claims description 4
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 4
- 229930006000 Sucrose Natural products 0.000 claims description 4
- 241000209140 Triticum Species 0.000 claims description 4
- 235000021307 Triticum Nutrition 0.000 claims description 4
- RHZUVFJBSILHOK-UHFFFAOYSA-N anthracen-1-ylmethanolate Chemical compound C1=CC=C2C=C3C(C[O-])=CC=CC3=CC2=C1 RHZUVFJBSILHOK-UHFFFAOYSA-N 0.000 claims description 4
- 239000003830 anthracite Substances 0.000 claims description 4
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 4
- 239000003822 epoxy resin Substances 0.000 claims description 4
- 229920005546 furfural resin Polymers 0.000 claims description 4
- 239000003077 lignite Substances 0.000 claims description 4
- 235000014571 nuts Nutrition 0.000 claims description 4
- 229920000647 polyepoxide Polymers 0.000 claims description 4
- 239000007790 solid phase Substances 0.000 claims description 4
- 239000008107 starch Substances 0.000 claims description 4
- 235000019698 starch Nutrition 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 239000010902 straw Substances 0.000 claims description 4
- 239000005720 sucrose Substances 0.000 claims description 4
- 235000020234 walnut Nutrition 0.000 claims description 4
- 239000007773 negative electrode material Substances 0.000 claims description 2
- 240000007049 Juglans regia Species 0.000 claims 1
- 238000010438 heat treatment Methods 0.000 description 24
- 239000003792 electrolyte Substances 0.000 description 16
- 230000002829 reductive effect Effects 0.000 description 15
- 239000000463 material Substances 0.000 description 13
- 230000007547 defect Effects 0.000 description 12
- 239000012528 membrane Substances 0.000 description 12
- 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 9
- 230000000694 effects Effects 0.000 description 9
- 239000010410 layer Substances 0.000 description 9
- 229910052708 sodium Inorganic materials 0.000 description 9
- 239000011734 sodium Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 230000002427 irreversible effect Effects 0.000 description 8
- 238000004080 punching Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 238000000354 decomposition reaction Methods 0.000 description 6
- 239000011229 interlayer Substances 0.000 description 6
- 239000012299 nitrogen atmosphere Substances 0.000 description 6
- 238000003860 storage Methods 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 4
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 4
- 239000011889 copper foil Substances 0.000 description 4
- 229910001873 dinitrogen Inorganic materials 0.000 description 4
- 239000011565 manganese chloride Substances 0.000 description 4
- 235000002867 manganese chloride Nutrition 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 230000002441 reversible effect Effects 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- 241000758789 Juglans Species 0.000 description 3
- 239000010406 cathode material Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000000428 dust Substances 0.000 description 3
- 239000002023 wood Substances 0.000 description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- 238000001069 Raman spectroscopy Methods 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 238000009656 pre-carbonization Methods 0.000 description 2
- 230000008707 rearrangement Effects 0.000 description 2
- 241000167854 Bourreria succulenta Species 0.000 description 1
- 238000001237 Raman spectrum Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 235000019693 cherries Nutrition 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000010903 husk Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000029058 respiratory gaseous exchange Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- 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
- C01B32/20—Graphite
- C01B32/205—Preparation
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a preparation method of a sodium ion battery anode material with high first efficiency, which comprises the following steps: s1 pre-carbonizing a carbon source: performing low-temperature sintering pretreatment on a carbon source to obtain a carbon precursor; s2, mixing: mixing a carbon precursor with a metal cation catalyst to obtain a mixed precursor; s3, graphitizing at low temperature: carrying out low-temperature catalytic graphitization on the mixed precursor to obtain a surface graphitized carbon precursor; s4, acid washing to remove the catalyst: removing the metal catalyst on the surface of the carbon precursor by using an acid washing process, and finally washing with water until the pH value is neutral to obtain a purified surface graphitized carbon precursor; s5, high-temperature carbonization: and (3) placing the purified surface graphitized carbon precursor obtained in the step (S4) in a high-temperature carbonization furnace, and performing high-temperature sintering in a protective gas atmosphere to obtain the sodium ion battery negative electrode hard carbon material. The preparation method of the sodium ion battery anode material with high first efficiency has the characteristics of high first efficiency and excellent multiplying power performance.
Description
Technical Field
The invention relates to the technical field of sodium ion batteries, in particular to a preparation method of a sodium ion battery anode material with high first efficiency.
Background
In recent years, along with the rapid rise of the price of lithium carbonate and the fire explosion of the energy storage market, sodium ion batteries are attracting attention, and industrialization thereof is entering a rapid development stage.
The hard carbon material has the advantages of wide raw material source, abundant resources and low price, and is used for the negative electrode of the sodium ion battery, and has higher sodium storage capacity, lower sodium storage potential and good cycling stability, so the hard carbon material is considered as the sodium storage negative electrode material with the most application prospect.
But the relatively low first effect properties of hard carbon materials prevent their better application. At present, aiming at the problem of lower initial effect of a hard carbon material, a mode of reducing the specific surface area of the hard carbon material, such as surface coating, is mostly adopted. By reducing the contact area of the hard carbon material and the electrolyte, the irreversible decomposition of the electrolyte is reduced, and thus the irreversible capacity loss is reduced. However, the smaller the specific surface area of the hard carbon material, the smaller the contact area with the electrolyte, and the fewer channels for sodium ions to migrate into the inside of the carbon material, resulting in poor rate performance. Therefore, the irreversible reaction between the hard carbon material and the electrolyte is reduced while the sufficient specific surface area is ensured, has important significance for the development of hard carbon materials.
The existing hard carbon material has the problem of low first-week coulomb efficiency, and seriously hinders the industrialized development of sodium ion batteries. At present, the specific surface area of the hard carbon material is reduced by adopting modes such as surface coating and the like, the contact area between the hard carbon material and the electrolyte is reduced, the irreversible decomposition of the electrolyte is further reduced, and the first-week coulomb efficiency of the hard carbon material is improved. However, a smaller specific surface area results in a reduced number of channels for sodium ions to migrate into the interior of the carbon material, resulting in poor rate performance. .
Disclosure of Invention
The invention aims to provide a preparation method of a sodium ion battery anode material with high first efficiency, which has the characteristics of high first efficiency and excellent multiplying power performance.
The invention can be realized by the following technical scheme:
the invention discloses a preparation method of a sodium ion battery anode material with high first efficiency, which comprises the following steps:
s1, pre-carbonizing a carbon source: placing a carbon source in a low-temperature carbonization furnace, and performing low-temperature sintering pretreatment in a protective gas atmosphere to obtain a carbon precursor;
s2, mixing: mixing the carbon precursor obtained in the step S1 with a metal cation catalyst with a graphitization catalysis function to obtain a mixed precursor;
s3, graphitizing at low temperature: placing the mixed precursor obtained in the step S2 in a low-temperature carbonization furnace, and performing low-temperature catalytic graphitization in a protective gas atmosphere to obtain a surface graphitized carbon precursor;
s4, acid washing to remove the catalyst: removing the metal catalyst on the surface of the surface graphitized carbon precursor obtained in the step S3 by using an acid washing process, and finally washing with water until the pH value is neutral to obtain a purified surface graphitized carbon precursor;
s5, high-temperature carbonization: and (3) placing the purified surface graphitized carbon precursor obtained in the step (S4) in a high-temperature carbonization furnace, and performing high-temperature sintering in a protective gas atmosphere to obtain the sodium ion battery negative electrode hard carbon material.
The invention aims at the problems that in the prior art, a large number of defects exist on the surface of a hard carbon material, and in the battery cycle process, the surface defects catalyze irreversible decomposition of electrolyte, so that the initial coulomb efficiency is reduced, and the capacity of the battery is reduced due to sodium ions lost in the process of being applied to a full battery. By adopting the preparation method of the invention, by reducing the surface defect degree of the material without reducing the contact area between the material and the electrolyte, the irreversible decomposition of the electrolyte is reduced, and the first-week coulomb efficiency and the rate capability of the hard carbon anode material are further improved.
Further, in step S1, the carbon source is one or more of anthracite, lignite, wood dust powder, walnut shell powder, coffee shell powder, nut shell powder, wheat straw powder, phenolic resin, epoxy resin, furfural resin, glucose, sucrose and starch.
Further, in step S1, the conditions for the pretreatment are: the temperature rising rate is 5-20 ℃/min, the pretreatment temperature is 250-500 ℃, and the pretreatment time is 2-5 h; the shielding gas is nitrogen and/or argon. In the present invention, the purpose of the low temperature treatment of step S1 is to achieve a certain degree of carbonization of the carbon source, but graphitization is not started. The pre-carbonization temperature affects the effect of the present invention. Specifically, if the pretreatment temperature is too high, graphitization of the carbon precursor has already begun; if the pretreatment temperature is too low, the carbon precursor is not fully formed into carbon, which is unfavorable for the subsequent catalytic graphitization process, and the effect of the invention is not achieved.
Further, in step S2, the metal cation catalyst includes Fe 2+ 、Fe 3+ 、Co 2+ 、Ni 2+ 、Ca 2+ 、Mg 2+ 、Zn 2 + 、Mn 2+ 、Sn 2+ And/or Sn 4+ One or more than two of them; the addition amount of the metal cation catalyst is 0.5-2.5% of the addition mass of the carbon precursor.
Further, in step S2, the mixing mode is liquid phase mixing and/or solid phase mixing; the uniform mixing is performed by ball milling, sand milling and/or stirring.
Further, in step S3, the conditions for low temperature graphitization are: the temperature rising rate is 0.5-5 ℃/min, the graphitization temperature is 500-900 ℃, and the catalytic graphitization time is 1-5 h. In step S3, the metal cations may catalyze the carbon material surface SP 3 Carbon orientation SP 2 The conversion of carbon, and further the formation and ordered rearrangement of a graphite layer are promoted, so that the defect degree of the surface of the carbon material is effectively reduced. In the invention, the temperature of low-temperature graphitization influences the microstructure of the surface of the hard carbon material, thereby influencing the electrochemical performance of the hard carbon material. Specifically, if the graphitization temperature is too low, the activity of the catalyst is insufficient, and the aim of catalyzing the graphitization of the surface of the hard carbon material and reducing the defect degree is not achieved; if the graphitization temperature is too high, the graphitization degree of the surface of the material is too high, the interlayer spacing is narrowed, the transmission of sodium ions is not facilitated, and the multiplying power performance of the material is affected.
Further, in step S4, the acid used is HCl, H 2 SO 4 、HNO 3 、HF、One or more of oxalic acid and/or formic acid; the pickling temperature is 40-85 DEG C
Further, in step S5, the conditions of high-temperature carbonization are: the temperature rising rate is 0.5-5 ℃/min, the carbonization temperature is 1000-1600 ℃, and the carbonization time is 2-10 h. In the present invention, the high temperature carbonization temperature also affects the structure and performance of the hard carbon material. Specifically, if the high-temperature sintering temperature is insufficient, the graphitization degree of the inside of the hard carbon material is low, and sufficient interlayer embedded sodium storage sites cannot be formed; too high a carbonization temperature will result in too narrow an interlayer spacing of the carbon layers in the hard carbon material, which is detrimental to sodium ion migration in the hard carbon material, affecting the electrochemical properties of the hard carbon material.
The invention also provides a sodium ion battery cathode material, which is prepared by the preparation method.
The preparation method of the sodium ion battery anode material with high first efficiency has the following beneficial effects:
the first and first cycle coulomb efficiency is high, and the first cycle coulomb efficiency of the hard carbon material is improved by catalyzing graphitization on the surface of the hard carbon material by metal cations, so that the surface defect degree of the material is reduced, the irreversible decomposition of electrolyte on the surface of the hard carbon material is reduced, and the first cycle coulomb efficiency of the hard carbon material is improved;
secondly, the method has excellent multiplying power performance, reduces the surface defect degree of the material by catalyzing graphitization on the surface of the hard carbon material by metal cations, does not reduce the specific surface area of the hard carbon material, ensures the contact area of the hard carbon material and electrolyte, ensures sufficient passage of sodium ions for transmitting into the hard carbon material, and further improves the multiplying power performance of the hard carbon material.
Detailed Description
In order to better understand the technical solution of the present invention, the following describes the product of the present invention in further detail with reference to examples.
The invention discloses a preparation method of a sodium ion battery anode material with high first efficiency, which comprises the following steps:
s1, pre-carbonizing a carbon source: placing a carbon source in a low-temperature carbonization furnace, and performing low-temperature sintering pretreatment in a protective gas atmosphere to obtain a carbon precursor;
s2, mixing: mixing the carbon precursor obtained in the step S1 with a metal cation catalyst with a graphitization catalysis function to obtain a mixed precursor;
s3, graphitizing at low temperature: placing the mixed precursor obtained in the step S2 in a low-temperature carbonization furnace, and performing low-temperature catalytic graphitization in a protective gas atmosphere to obtain a surface graphitized carbon precursor;
s4, acid washing to remove the catalyst: removing the metal catalyst on the surface of the surface graphitized carbon precursor obtained in the step S3 by using an acid washing process, and finally washing with water until the pH value is neutral to obtain a purified surface graphitized carbon precursor;
s5, high-temperature carbonization: and (3) placing the purified surface graphitized carbon precursor obtained in the step (S4) in a high-temperature carbonization furnace, and performing high-temperature sintering in a protective gas atmosphere to obtain the sodium ion battery negative electrode hard carbon material.
Further, in step S1, the carbon source is one or more of anthracite, lignite, wood dust powder, walnut shell powder, coffee shell powder, nut shell powder, wheat straw powder, phenolic resin, epoxy resin, furfural resin, glucose, sucrose and starch.
Further, in step S1, the conditions for the pretreatment are: the temperature rising rate is 5-20 ℃/min, the pretreatment temperature is 250-500 ℃, and the pretreatment time is 2-5 h; the shielding gas is nitrogen and/or argon. In the present invention, the purpose of the low temperature treatment of step S1 is to achieve a certain degree of carbonization of the carbon source, but graphitization is not started. The pre-carbonization temperature affects the effect of the present invention. Specifically, if the pretreatment temperature is too high, graphitization of the carbon precursor has already begun; if the pretreatment temperature is too low, the carbon precursor is not fully formed into carbon, which is unfavorable for the subsequent catalytic graphitization process, and the effect of the invention is not achieved.
Further, in step S2, the metal cation catalyst includes Fe 2+ 、Fe 3+ 、Co 2+ 、Ni 2+ 、Ca 2+ 、Mg 2+ 、Zn 2 + 、Mn 2+ 、Sn 2+ And/or Sn 4+ One or more than two of them; metal cation catalysisThe addition amount of the chemical agent is 0.5-2.5% of the addition mass of the carbon precursor.
Further, in step S2, the mixing mode is liquid phase mixing and/or solid phase mixing; the uniform mixing is performed by ball milling, sand milling and/or stirring.
Further, in step S3, the conditions for low temperature graphitization are: the temperature rising rate is 0.5-5 ℃/min, the graphitization temperature is 500-900 ℃, and the catalytic graphitization time is 1-5 h. In step S3, the metal cations may catalyze the carbon material surface SP 3 Carbon orientation SP 2 The conversion of carbon, and further the formation and ordered rearrangement of a graphite layer are promoted, so that the defect degree of the surface of the carbon material is effectively reduced. In the invention, the temperature of low-temperature graphitization influences the microstructure of the surface of the hard carbon material, thereby influencing the electrochemical performance of the hard carbon material. Specifically, if the graphitization temperature is too low, the activity of the catalyst is insufficient, and the aim of catalyzing the graphitization of the surface of the hard carbon material and reducing the defect degree is not achieved; if the graphitization temperature is too high, the graphitization degree of the surface of the material is too high, the interlayer spacing is narrowed, the transmission of sodium ions is not facilitated, and the multiplying power performance of the material is affected.
Further, in step S4, the acid is HCl, H 2 SO 4 、HNO 3 One or more of HF, oxalic acid and/or formic acid; the pickling temperature is 40-85 DEG C
Further, in step S5, the conditions of high-temperature carbonization are: the temperature rising rate is 0.5-5 ℃/min, the carbonization temperature is 1000-1600 ℃, and the carbonization time is 2-10 h. In the present invention, the high temperature carbonization temperature also affects the structure and performance of the hard carbon material. Specifically, if the high-temperature sintering temperature is insufficient, the graphitization degree of the inside of the hard carbon material is low, and sufficient interlayer embedded sodium storage sites cannot be formed; too high a carbonization temperature will result in too narrow an interlayer spacing of the carbon layers in the hard carbon material, is unfavorable for the migration of sodium ions in the hard carbon material, and affects the electrochemical performance of the hard carbon material.
The invention also provides a sodium ion battery cathode material, which is prepared by the preparation method.
Example 1
The embodiment discloses a preparation method of a sodium ion battery anode material with high first efficiency, which comprises the following steps:
s1, pre-carbonizing a carbon source: placing a carbon source in a low-temperature carbonization furnace, and performing low-temperature sintering pretreatment in a protective gas atmosphere to obtain a carbon precursor;
s2, mixing: mixing the carbon precursor obtained in the step S1 with a metal cation catalyst with a graphitization catalysis function to obtain a mixed precursor;
s3, graphitizing at low temperature: placing the mixed precursor obtained in the step S2 in a low-temperature carbonization furnace, and performing low-temperature catalytic graphitization in a protective gas atmosphere to obtain a surface graphitized carbon precursor;
s4, acid washing to remove the catalyst: removing the metal catalyst on the surface of the surface graphitized carbon precursor obtained in the step S3 by using an acid washing process, and finally washing with water until the pH value is neutral to obtain a purified surface graphitized carbon precursor;
s5, high-temperature carbonization: and (3) placing the purified surface graphitized carbon precursor obtained in the step (S4) in a high-temperature carbonization furnace, and performing high-temperature sintering in a protective gas atmosphere to obtain the sodium ion battery negative electrode hard carbon material.
In the embodiment, in step S1, the carbon source is anthracite or lignite. The pretreatment conditions are as follows: the temperature rising rate is 20 ℃/min, the pretreatment temperature is 360 ℃, and the pretreatment time is 2 h; the shielding gas is nitrogen.
In the present embodiment, in step S2, the metal cation catalyst includes Fe 2+ 、Fe 3+ The method comprises the steps of carrying out a first treatment on the surface of the The addition amount of the metal cation catalyst is 2.5% of the addition mass of the carbon precursor; the mixing mode is liquid phase mixing; the mode of uniform mixing is ball milling.
In this embodiment, in step S3, the conditions for low temperature graphitization are: the temperature rising rate is 5 ℃/min, the graphitization temperature is 700 ℃, and the catalytic graphitization time is 1h.
In this example, in step S4, the acid used is HCl, H 2 SO 4 The method comprises the steps of carrying out a first treatment on the surface of the The pickling temperature is 85 DEG C
In this embodiment, in step S5, the conditions for high temperature carbonization are: the temperature rising rate is 5 ℃/min, the carbonization temperature is 1300 ℃, and the carbonization time is 2 h.
Example 2
The embodiment discloses a preparation method of a sodium ion battery anode material with high first efficiency, which comprises the following steps:
s1, pre-carbonizing a carbon source: placing a carbon source in a low-temperature carbonization furnace, and performing low-temperature sintering pretreatment in a protective gas atmosphere to obtain a carbon precursor;
s2, mixing: mixing the carbon precursor obtained in the step S1 with a metal cation catalyst with a graphitization catalysis function to obtain a mixed precursor;
s3, graphitizing at low temperature: placing the mixed precursor obtained in the step S2 in a low-temperature carbonization furnace, and performing low-temperature catalytic graphitization in a protective gas atmosphere to obtain a surface graphitized carbon precursor;
s4, acid washing to remove the catalyst: removing the metal catalyst on the surface of the surface graphitized carbon precursor obtained in the step S3 by using an acid washing process, and finally washing with water until the pH value is neutral to obtain a purified surface graphitized carbon precursor;
s5, high-temperature carbonization: and (3) placing the purified surface graphitized carbon precursor obtained in the step (S4) in a high-temperature carbonization furnace, and performing high-temperature sintering in a protective gas atmosphere to obtain the sodium ion battery negative electrode hard carbon material.
In this embodiment, in step S1, the carbon source is wood dust powder or walnut shell powder. The pretreatment conditions are as follows: the heating rate is 12 ℃/min, the pretreatment temperature is 250 ℃, and the pretreatment time is 5 h; protective gas is argon.
In this embodiment, in step S2, the metal cation catalyst includes Co 2+ 、Ni 2+ The method comprises the steps of carrying out a first treatment on the surface of the The addition amount of the metal cation catalyst is 1.5% of the addition mass of the carbon precursor; the mixing mode is liquid-solid phase mixing; the mode of uniform mixing is sand milling.
In this embodiment, in step S3, the conditions for low temperature graphitization are: the temperature rising rate is 3 ℃/min, the graphitization temperature is 500 ℃, and the catalytic graphitization time is 5 h.
In this embodiment, in step S4, the acid used is HNO 3 HF; the pickling temperature is 65 DEG C
In this embodiment, in step S5, the conditions for high temperature carbonization are: the heating rate is 3 ℃/min, the carbonization temperature is 1000 ℃, and the carbonization time is 10 h.
Example 3
The embodiment discloses a preparation method of a sodium ion battery anode material with high first efficiency, which comprises the following steps:
s1, pre-carbonizing a carbon source: placing a carbon source in a low-temperature carbonization furnace, and performing low-temperature sintering pretreatment in a protective gas atmosphere to obtain a carbon precursor;
s2, mixing: mixing the carbon precursor obtained in the step S1 with a metal cation catalyst with a graphitization catalysis function to obtain a mixed precursor;
s3, graphitizing at low temperature: placing the mixed precursor obtained in the step S2 in a low-temperature carbonization furnace, and performing low-temperature catalytic graphitization in a protective gas atmosphere to obtain a surface graphitized carbon precursor;
s4, acid washing to remove the catalyst: removing the metal catalyst on the surface of the carbon precursor with graphitized surface obtained in the step S3 by using an acid washing process, finally, washing with water until the pH value is neutral, and obtaining a purified surface graphitized carbon precursor;
s5, high-temperature carbonization: and (3) placing the purified surface graphitized carbon precursor obtained in the step (S4) in a high-temperature carbonization furnace, and performing high-temperature sintering in a protective gas atmosphere to obtain the sodium ion battery negative electrode hard carbon material.
In this embodiment, in step S1, the carbon source is coffee cherry husks powder, nut shell powder, wheat straw powder. Pretreated(s) the conditions are as follows: the temperature rising rate is 5 ℃/min, the pretreatment temperature is 500 ℃, and the pretreatment time is 3.5 h; the shielding gas is nitrogen and argon.
In this embodiment, in step S2, the metal cation catalyst includes Ca 2+ 、Mg 2+ 、Zn 2+ 、Mn 2+ The method comprises the steps of carrying out a first treatment on the surface of the The addition amount of the metal cation catalyst is 0.5% of the addition mass of the carbon precursor; the mixing mode is liquid phase mixing; the mode of uniform mixing is stirring.
In this embodiment, in step S3, the conditions for low temperature graphitization are: the temperature rising rate is 0.5 ℃/min, the graphitization temperature is 900 ℃, and the catalytic graphitization time is 3 h.
In this example, in step S4, the acids used are oxalic acid and formic acid; the pickling temperature is 40 DEG C
In this embodiment, in step S5, the conditions for high temperature carbonization are: the temperature rising rate is 0.5 ℃/min, the carbonization temperature is 1600 ℃, and the carbonization time is 6 h.
Example 4
The embodiment discloses a preparation method of a sodium ion battery anode material with high first efficiency, which comprises the following steps:
s1, pre-carbonizing a carbon source: placing a carbon source in a low-temperature carbonization furnace, and performing low-temperature sintering pretreatment in a protective gas atmosphere to obtain a carbon precursor;
s2, mixing: mixing the carbon precursor obtained in the step S1 with a metal cation catalyst with a graphitization catalysis function, obtaining a mixed precursor;
s3, graphitizing at low temperature: placing the mixed precursor obtained in the step S2 in a low-temperature carbonization furnace, and performing low-temperature catalytic graphitization in a protective gas atmosphere to obtain a surface graphitized carbon precursor;
s4, acid washing to remove the catalyst: removing the metal catalyst on the surface of the surface graphitized carbon precursor obtained in the step S3 by using an acid washing process, and finally washing with water until the pH value is neutral to obtain a purified surface graphitized carbon precursor;
s5, high-temperature carbonization: and (3) placing the purified surface graphitized carbon precursor obtained in the step (S4) in a high-temperature carbonization furnace, and performing high-temperature sintering in a protective gas atmosphere to obtain the sodium ion battery negative electrode hard carbon material.
In the embodiment, in step S1, the carbon source is phenolic resin, epoxy resin, furfural resin, glucose, sucrose, starch. The pretreatment conditions are as follows: the heating rate is 10 ℃/min, the pretreatment temperature is 400 ℃, and the pretreatment time is 3 h; the shielding gas is nitrogen and argon.
In the present embodiment, in step S2, the metal cation catalyst includes Fe 2+ 、Fe 3+ 、Mn 2+ 、Sn 2+ The method comprises the steps of carrying out a first treatment on the surface of the The addition amount of the metal cation catalyst is 1.5% of the addition mass of the carbon precursor; the mixing mode is that mixing liquid phase; the mode of uniform mixing is sand milling.
In this embodiment, in step S3, the conditions for low temperature graphitization are: the temperature rising rate is 3 ℃/min, the graphitization temperature is 600 ℃, and the catalytic graphitization time is 4 h.
In this example, in step S4, the acids used are oxalic acid and formic acid; the pickling temperature is 65 DEG C
In this embodiment, in step S5, the conditions for high temperature carbonization are: the heating rate is 2 ℃/min, the carbonization temperature is 1200 ℃, and the carbonization time is 5 h.
Application example 1
The preparation method of the sodium ion battery cathode material of the embodiment, the method comprises the following steps:
s1, pre-carbonizing a carbon source: and (3) placing the phenolic resin in a low-temperature carbonization furnace, heating to 500 ℃ at a heating rate of 5 ℃/min in a nitrogen atmosphere, and preserving heat for 2 hours to obtain the carbon precursor.
S2, uniformly mixing the carbon precursor in the step S1 with FeCl3 to obtain a mixed precursor. Wherein the addition amount of FeCl3 is 1% of the mass of the carbon precursor, and the mixing mode is planetary ball milling.
S3, graphitizing at low temperature: placing the mixed precursor obtained in the step S2 into a low-temperature carbonization furnace, heating to 600 ℃ at a heating rate of 2 ℃/min in a nitrogen gas atmosphere, and preserving heat for 2h to obtain a surface graphitized carbon precursor;
s4, acid washing to remove the catalyst: carrying out acid washing treatment on the surface graphitized carbon precursor in the step S3 by using HCl solution at 60 ℃, and then washing the surface graphitized carbon precursor to be neutral by water to obtain a purified surface graphitized carbon precursor;
s5, high-temperature carbonization: and (3) placing the purified surface graphitized carbon precursor obtained in the step (S4) in a high-temperature carbonization furnace, heating to 1500 ℃ at a heating rate of 1 ℃/min in a nitrogen gas atmosphere, and preserving heat for 2h to obtain the sodium ion battery negative electrode hard carbon material.
The resulting material was subjected to electrochemical performance testing according to the following method: after the S-doped hard carbon material, super P, CMC and SBR are mixed into homogenate according to the mass ratio of 94:1.5:2:2.5, a 120 um four-side preparation machine is used for coating black paste on copper foil, and then the film is dried in a vacuum drying oven at 100 ℃ for 2 hours. And (3) punching the electrode film to a circular sheet with the radius of 0.6mm by using a sheet punching machine, taking metal sodium as a counter electrode, taking 1mol/L NaClO4EC+DEC (1:1vol%) as electrolyte, and assembling the membrane into the CR2016 type button cell in a glove box, wherein the membrane is a PP/PE/PP three-layer membrane. The button cell was subjected to constant current charge and discharge test at a current density of 0.1C (1c=300 mAh/g) and a voltage range of 2 to 0.005V.
Comparative example 1
The preparation method of the sodium ion battery anode material comprises the following steps:
s1, pre-carbonizing a carbon source: and (3) placing the phenolic resin in a low-temperature carbonization furnace, heating to 500 ℃ at a heating rate of 5 ℃/min in a nitrogen atmosphere, and preserving heat for 2 hours to obtain the carbon precursor.
S2, high-temperature carbonization: and (2) placing the carbon precursor obtained in the step (S2) in a high-temperature carbonization furnace, heating to 1500 ℃ at a heating rate of 1 ℃/min in a nitrogen atmosphere, and preserving heat for 2h to obtain the sodium ion battery negative electrode hard carbon material.
The resulting material was subjected to electrochemical performance testing according to the following method: after the S-doped hard carbon material, super P, CMC and SBR are mixed into homogenate according to the mass ratio of 94:1.5:2:2.5, a 120 um four-side preparation machine is used for coating black paste on copper foil, and then the film is dried in a vacuum drying oven at 100 ℃ for 2 hours. And (3) punching the electrode film to a circular sheet with the radius of 0.6mm by using a sheet punching machine, taking metal sodium as a counter electrode, taking 1mol/L NaClO4EC+DEC (1:1vol%) as electrolyte, and assembling the membrane into the CR2016 type button cell in a glove box, wherein the membrane is a PP/PE/PP three-layer membrane. The button cell was subjected to constant current charge and discharge test at a current density of 0.1C (1c=300 mAh/g) and a voltage range of 2 to 0.005V.
Application example 2
The preparation method of the sodium ion battery anode material comprises the following steps:
s1, pre-carbonizing a carbon source: and (3) placing glucose into a low-temperature carbonization furnace, heating to 400 ℃ at a heating rate of 5 ℃/min in a nitrogen atmosphere, and preserving heat for 2 hours to obtain a carbon precursor.
S2, uniformly mixing the carbon precursor in the step S1 with MnCl2 to obtain a mixed precursor. Wherein the addition amount of MnCl2 is 0.8% of the mass of the carbon precursor, and the mixing mode is planetary ball milling.
S3, graphitizing at low temperature: placing the mixed precursor obtained in the step S2 into a low-temperature carbonization furnace, heating to 800 ℃ at a heating rate of 2 ℃/min in a nitrogen gas atmosphere, and preserving heat for 2h to obtain a surface graphitized carbon precursor;
s4, acid washing to remove the catalyst: carrying out acid washing treatment on the surface graphitized carbon precursor in the step S3 by using HCl solution at 60 ℃, and then washing the surface graphitized carbon precursor to be neutral by water to obtain a purified surface graphitized carbon precursor;
s5, high-temperature carbonization: and (3) placing the purified surface graphitized carbon precursor obtained in the step (S4) in a high-temperature carbonization furnace, heating to 1300 ℃ at a heating rate of 1 ℃/min in a nitrogen gas atmosphere, and preserving heat for 2h to obtain the sodium ion battery negative electrode hard carbon material.
The resulting material was subjected to electrochemical performance testing according to the following method: after the S-doped hard carbon material, super P, CMC and SBR are mixed into homogenate according to the mass ratio of 94:1.5:2:2.5, a 120 um four-side preparation machine is used for coating black paste on copper foil, and then the film is dried in a vacuum drying oven at 100 ℃ for 2 hours. And (3) punching the electrode film to a circular sheet with the radius of 0.6mm by using a sheet punching machine, taking metal sodium as a counter electrode, taking 1mol/L NaClO4EC+DEC (1:1vol%) as electrolyte, and assembling the membrane into the CR2016 type button cell in a glove box, wherein the membrane is a PP/PE/PP three-layer membrane. The button cell was subjected to constant current charge and discharge test at a current density of 0.1C (1c=300 mAh/g) and a voltage range of 2 to 0.005V.
Comparative example 2
The preparation method of the sodium ion battery anode material comprises the following steps:
s1, pre-carbonizing a carbon source: and (3) placing glucose into a low-temperature carbonization furnace, heating to 400 ℃ at a heating rate of 5 ℃/min in a nitrogen atmosphere, and preserving heat for 2 hours to obtain a carbon precursor.
S2, uniformly mixing the carbon precursor in the step S1 with MnCl2, to obtain a mixed precursor. Wherein the addition amount of MnCl2 is 0.8% of the mass of the carbon precursor, and the mixing mode is planetary ball milling.
S2, high-temperature carbonization: and (2) placing the carbon precursor obtained in the step (S1) in a high-temperature carbonization furnace, heating to 1300 ℃ at a heating rate of 1 ℃/min in a nitrogen atmosphere, and preserving heat for 2h to obtain the sodium ion battery negative electrode hard carbon material.
The resulting material was subjected to electrochemical performance testing according to the following method: after the S-doped hard carbon material, super P, CMC and SBR are mixed into homogenate according to the mass ratio of 94:1.5:2:2.5, a 120 um four-side preparation machine is used for coating black paste on copper foil, and then the film is dried in a vacuum drying oven at 100 ℃ for 2 hours. And (3) punching the electrode film to a circular sheet with the radius of 0.6mm by using a sheet punching machine, taking metal sodium as a counter electrode, taking 1mol/L NaClO4EC+DEC (1:1vol%) as electrolyte, and assembling the membrane into the CR2016 type button cell in a glove box, wherein the membrane is a PP/PE/PP three-layer membrane. The button cell was subjected to constant current charge and discharge test at a current density of 0.1C (1c=300 mAh/g) and a voltage range of 2 to 0.005V.
The Raman spectrum of the carbon material is 1340-1340 cm -1 (peak D) and 1590 cm -1 Two characteristic peaks are shown at (G peak), wherein the D peak is derived from A1G vibration mode caused by carbon layer defect and ring respiration vibration of sp2 carbon atoms in the six-membered ring at the edge; and the G peak is derived from an E2G vibration mode caused by in-plane stretching vibration of sp2 carbon atoms in a ring or a chain. Id/Ig can therefore be used to characterize the extent of defects in the carbon material.
As shown in Table 1, the Id/Ig values of the hard carbon materials in example 1 and comparative example 1 were 1.03 and 1.22, respectively, as measured by Raman spectroscopy. The BET specific surface area values of the hard carbon materials in example 1 and comparative example 1 were 13.3 and 10.5, respectively, as measured by a specific surface analyzer. The reversible specific capacity of the electrode of application example 1 is 322 mAh/g, and the first week coulomb efficiency is 94%; the reversible specific capacity of the electrode of comparative example 1 was only 310 mAh/g, and the first week coulombic efficiency was only 89%.
As shown in Table 1, the Id/Ig values of the hard carbon materials in example 2 and comparative example 2 were 1.10 and 1.25, respectively, as measured by Raman spectroscopy. The BET specific surface area values of the hard carbon materials in example 2 and comparative example 2 were 18.4 and 14.1, respectively, as measured by a specific surface analyzer. The reversible specific capacity of the electrode of application example 2 is 314 mAh/g, and the first week coulomb efficiency is 93%; the reversible specific capacity of the electrode of comparative example 2 was only 308 mAh/g, and the first week coulombic efficiency was only 86%.
The root cause of the first effect improvement of the application example 1 and the application example 2 is that the metal cations catalyze the graphitization of the surface of the hard carbon material, so that the defect degree of the surface of the carbon material is reduced, the irreversible decomposition of the electrolyte on the surface of the material is inhibited, and the first effect of the hard carbon material is further improved.
TABLE 1 Performance test results
The foregoing examples are merely exemplary embodiments of the present invention, which are described in more detail and are not to be construed as limiting the scope of the invention. It should be noted that modifications and improvements can be made by those skilled in the art without departing from the spirit of the invention, and that these obvious alternatives fall within the scope of the invention.
Claims (9)
1. The preparation method of the sodium ion battery anode material with high first efficiency is characterized by comprising the following steps of:
s1, pre-carbonizing a carbon source: placing a carbon source in a low-temperature carbonization furnace, and performing low-temperature sintering pretreatment in a protective gas atmosphere to obtain a carbon precursor;
s2, mixing: mixing the carbon precursor obtained in the step S1 with a metal cation catalyst with a graphitization catalysis function to obtain a mixed precursor;
s3 and (3) graphitizing at low temperature: placing the mixed precursor obtained in the step S2 in a low-temperature carbonization furnace, and performing low-temperature catalytic graphitization in a protective gas atmosphere to obtain a surface graphitized carbon precursor;
s4, acid washing to remove the catalyst: removing the metal catalyst on the surface of the surface graphitized carbon precursor obtained in the step S3 by using an acid washing process, and finally washing with water until the pH value is neutral to obtain a purified surface graphitized carbon precursor;
s5, high-temperature carbonization: and (3) placing the purified surface graphitized carbon precursor obtained in the step (S4) in a high-temperature carbonization furnace, and performing high-temperature sintering in a protective gas atmosphere to obtain the sodium ion battery negative electrode hard carbon material.
2. The method for preparing the sodium ion battery anode material with high first efficiency according to claim 1, which is characterized in that: in the step S1, the carbon source is one or more of anthracite, lignite, sawdust powder, walnut shell powder, coffee shell powder, nut shell powder, wheat straw powder, phenolic resin, epoxy resin, furfural resin, glucose, sucrose and starch.
3. The method for preparing the sodium ion battery anode material with high first efficiency according to claim 1, which is characterized in that: in step S1, the conditions for the pretreatment are: the temperature rising rate is 5-20 ℃/min, the pretreatment temperature is 250-500 ℃, and the pretreatment time is 2-5 h; the shielding gas is nitrogen and/or argon.
4. The method for preparing the sodium ion battery anode material with high first efficiency according to claim 1, which is characterized in that: in step S2, the metal cation catalyst comprises Fe 2+ 、Fe 3+ 、Co 2+ 、Ni 2+ 、Ca 2+ 、Mg 2+ 、Zn 2+ 、Mn 2+ 、Sn 2+ And/or Sn 4+ One or more than two of them; the addition amount of the metal cation catalyst is 0.5-2.5% of the addition mass of the carbon precursor.
5. The method for preparing the sodium ion battery anode material with high first efficiency according to claim 1, which is characterized in that: in step S2, the mixing mode is liquid phase mixing and/or solid phase mixing; the uniform mixing is performed by ball milling, sand milling and/or stirring.
6. The method for preparing the sodium ion battery anode material with high first efficiency according to claim 1, which is characterized in that: in step S3, the conditions for low temperature graphitization are: the temperature rising rate is 0.5-5 ℃/min, the graphitization temperature is 500-900 ℃, and the catalytic graphitization time is 1-5 h.
7. First-time efficient sodium ions according to claim 1The preparation method of the sub-battery anode material is characterized by comprising the following steps: in step S4, the acid used is HCl, H 2 SO 4 、HNO 3 One or more of HF, oxalic acid and/or formic acid; the pickling temperature is 40-85 ℃.
8. The method for preparing the sodium ion battery anode material with high first efficiency according to claim 1, which is characterized in that: in step S5, the conditions of high temperature carbonization are: the temperature rising rate is 0.5-5 ℃/min, the carbonization temperature is 1000-1600 ℃, and the carbonization time is 2-10 h.
9. A negative electrode material of a sodium ion battery is characterized in that: is prepared by the preparation method of any one of claims 1-8.
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