CN118005004A - Hard carbon negative electrode material for sodium ion battery and preparation method thereof - Google Patents
Hard carbon negative electrode material for sodium ion battery and preparation method thereof Download PDFInfo
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- CN118005004A CN118005004A CN202410421691.6A CN202410421691A CN118005004A CN 118005004 A CN118005004 A CN 118005004A CN 202410421691 A CN202410421691 A CN 202410421691A CN 118005004 A CN118005004 A CN 118005004A
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- 229910021385 hard carbon Inorganic materials 0.000 title claims abstract description 40
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 22
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 239000007773 negative electrode material Substances 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 229920005610 lignin Polymers 0.000 claims abstract description 67
- 239000002243 precursor Substances 0.000 claims abstract description 19
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 18
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000003822 epoxy resin Substances 0.000 claims abstract description 17
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 17
- 239000011734 sodium Substances 0.000 claims abstract description 16
- 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 claims abstract description 12
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 239000004254 Ammonium phosphate Substances 0.000 claims abstract description 7
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims abstract description 7
- 235000019289 ammonium phosphates Nutrition 0.000 claims abstract description 7
- 230000001804 emulsifying effect Effects 0.000 claims abstract description 5
- 238000010000 carbonizing Methods 0.000 claims abstract description 4
- 239000002904 solvent Substances 0.000 claims abstract description 3
- 239000002253 acid Substances 0.000 claims description 21
- 238000010438 heat treatment Methods 0.000 claims description 16
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 13
- 150000007524 organic acids Chemical class 0.000 claims description 12
- 238000003763 carbonization Methods 0.000 claims description 11
- 239000004006 olive oil Substances 0.000 claims description 11
- 235000008390 olive oil Nutrition 0.000 claims description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- 239000010405 anode material Substances 0.000 claims description 5
- 235000019260 propionic acid Nutrition 0.000 claims description 5
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- YDEXUEFDPVHGHE-GGMCWBHBSA-L disodium;(2r)-3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfonatopropyl)phenoxy]propane-1-sulfonate Chemical compound [Na+].[Na+].COC1=CC=CC(C[C@H](CS([O-])(=O)=O)OC=2C(=CC(CCCS([O-])(=O)=O)=CC=2)OC)=C1O YDEXUEFDPVHGHE-GGMCWBHBSA-L 0.000 claims description 3
- 239000003921 oil Substances 0.000 claims description 3
- 235000019198 oils Nutrition 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 238000004945 emulsification Methods 0.000 claims 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 13
- 239000011229 interlayer Substances 0.000 abstract description 13
- 239000010439 graphite Substances 0.000 abstract description 9
- 229910002804 graphite Inorganic materials 0.000 abstract description 9
- 239000010410 layer Substances 0.000 abstract description 7
- 238000003860 storage Methods 0.000 abstract description 5
- 229920000642 polymer Polymers 0.000 abstract description 4
- 239000003795 chemical substances by application Substances 0.000 abstract description 3
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- 230000000052 comparative effect Effects 0.000 description 11
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- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 229910052698 phosphorus Inorganic materials 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 125000004429 atom Chemical group 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
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- 239000011148 porous material Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 239000002028 Biomass Substances 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
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- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 238000005554 pickling Methods 0.000 description 4
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
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- 239000012535 impurity Substances 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000004005 microsphere Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
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- 125000003118 aryl group Chemical group 0.000 description 2
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- 239000007833 carbon precursor Substances 0.000 description 2
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- 238000002441 X-ray diffraction Methods 0.000 description 1
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- ODLMAHJVESYWTB-UHFFFAOYSA-N propylbenzene Chemical group CCCC1=CC=CC=C1 ODLMAHJVESYWTB-UHFFFAOYSA-N 0.000 description 1
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- Battery Electrode And Active Subsutance (AREA)
Abstract
The application relates to the technical field of sodium ion batteries, and discloses a hard carbon negative electrode material for a sodium ion battery and a preparation method thereof; the preparation method comprises the following steps: treating lignin raw materials to obtain purified lignin; s2, in a solvent system, purifying lignin and ammonium phosphate/ammonium hydrogen phosphate, and emulsifying to obtain a precursor; and S3, curing and carbonizing the precursor and the epoxy resin to obtain the hard carbon material. The lignin provided by the application can cure the epoxy resin without any curing agent, so that an interpenetrating polymer network is formed, the formed carbon material has a stable structure, the number of the near-layer ordered graphite layers is increased, the interlayer spacing is large, and sodium storage is facilitated.
Description
Technical Field
The invention relates to the technical field of sodium ion batteries, in particular to a hard carbon negative electrode material for a sodium ion battery and a preparation method thereof.
Background
With the continuous development of science and technology economy, the demand of chemical non-renewable resources such as coal, petroleum and the like is increased, the problems of energy shortage, environmental pollution and the like are increased, and the development of clean, sustainable and environment-friendly energy is urgent. Renewable energy sources such as solar energy, wind energy and tidal energy are intermittent in production, and energy sources cannot be reliably provided on a large scale as required, so that large-scale energy storage equipment needs to be researched and developed to store and distribute intermittent renewable energy sources when required, wherein lithium ion batteries are widely applied to the energy storage field due to the fact that the lithium ion batteries have a series of advantages of high energy density, good multiplying power performance and the like, however, lithium resources are short and high in cost, and long-term application of the lithium ion batteries in the energy storage field is limited. Sodium has abundant reserves in nature, low development cost, the same main group as lithium on the periodic table of elements, and similar composition and working principles of sodium batteries and lithium batteries, so the sodium batteries are considered as candidate technologies with the most industrialization potential of large-scale power grid energy storage systems.
Graphite is used as a negative electrode material of a lithium ion battery, has good electrochemical performance, but cannot be used as a negative electrode material of a sodium ion battery, and because the radius of sodium is large, the graphite cannot be reversibly deintercalated, and the search for the negative electrode material with the deintercalated sodium ion is a key for the application of the sodium ion battery. The hard carbon has larger interlayer spacing, the inner carbon layers are arranged irregularly, and ideal active sites are provided for sodium ion storage by amorphous graphite sheets and nanopores; the biomass hard carbon anode material has wide application prospect in an electrochemical energy storage system because the biomass hard carbon anode material can retain the material structure and pore channels in a biomass template. Lignin is a three-dimensional aromatic amorphous high polymer formed by connecting three basic phenylpropane structures through ether bonds and carbon-carbon bonds, and is easily rearranged into a carbon six-membered ring network in the carbonization process due to a large number of benzene rings; is easier to graphitize compared with other natural polymers, and is beneficial to forming interlayer compounds. In the paper industry, tons of lignin are treated as waste (black liquor) or burned as low grade fuel, causing serious environmental pollution and resource waste problems. Meanwhile, the unrefined lignin contains a large amount of impurities, and is difficult to realize large-scale commercial application; these impurities affect lignin chemistry and storage properties to a large extent, and purification is necessary before development and utilization. When lignin is used for preparing a hard carbon precursor, a large number of defect sites and partial impurity residues are formed after heteroatom removal under high-temperature calcination, so that the irreversible capacity is large, and the first coulomb efficiency is low.
Patent publication No. CN116706034A discloses a hard carbon negative electrode material, a preparation method and application thereof, wherein a hard carbon precursor, a heteroatom precursor and a metal single atom precursor are dissolved in deionized water, the mixture is placed in a freeze dryer for freeze drying, the mixture is placed in a tube furnace for calcination to obtain a carbonized material, and finally the carbonized material is washed, filtered and dried to obtain the metal single atom doped hard carbon negative electrode material. In the technology, the metal atom clusters are doped in the holes of the hard carbon, so that electrochemical performances such as first efficiency and the like can be improved, but when the metal atom clusters are doped, metal atoms are not furthest exposed in the material, so that the advantages of activity and conductivity of the material cannot be fully exerted, and the effect of improving the electrical performance of the hard carbon cathode is limited.
Disclosure of Invention
The invention solves the technical problems that:
The method is used for solving the problem of low first coulombic efficiency existing in the current lignin-based hard carbon material.
The invention adopts the technical scheme that:
The invention aims to provide a hard carbon negative electrode material for a sodium ion battery and a preparation method thereof. The specific contents are as follows:
The application provides a preparation method of a hard carbon anode material for a sodium ion battery, which comprises the following steps:
s1, treating a lignin raw material to obtain purified lignin;
The specific contents are as follows:
the treatment comprises heat treatment and acid washing;
And (3) heat treatment: carrying out heat treatment on lignin raw materials and organic acid to obtain a pretreated substance; the mass ratio of the lignin raw material to the organic acid is 1:2-6; the organic acid comprises 40-60 wt% of acetic acid and propionic acid, wherein the preferable mass fraction is 40wt%, and the volume ratio of the acetic acid to the propionic acid is 1:1; the lignin raw material comprises at least one of sodium lignin sulfonate and sodium lignin sulfate.
The organic acid may increase the dissolution rate of lignin, which provides protons in solution to catalyze hydrolysis or reactions to break chemical bonds in lignin. The lipophilic nonpolar part of the organic acid can shield lignin and form micelle aggregates through pi-pi bond stacking or hydrophobic action to prevent lignin from reagglomerating, while the tail end of the hydrophilic part points outwards to water to realize effective dissolution of lignin, and when the organic acid is reduced to a certain concentration, the organic acid is insufficient to coat lignin, so that the solubility of lignin is reduced and the lignin is separated from the solution.
Acid washing: heating and rinsing the pretreated matter and the mixed acid liquor to obtain an acid-washed matter; dissolving and drying the acid washing matter to obtain purified lignin; the mixed acid liquid comprises hydrochloric acid, sulfuric acid and nitric acid; the mass ratio of the pretreatment to the mixed acid liquid is 1:1-5, and the volume ratio of the mixed acid liquid to the sulfuric acid is sulfuric acid=2:2:1; heating: 60-85 ℃ and 0.5-2 h.
The pretreated matter is crushed and ground, and then is heated, cooled and suction filtered with mixed acid liquid according to the mass ratio. Repeating the above pickling steps until the 3 rd pickling is completed. And (3) washing with acid, rinsing with hot water for multiple times until the pH value of the filtrate is 6-7, and finally drying the sample at 120 ℃ for 10 h to obtain the purified lignin.
S2, in a solvent system, purifying lignin, and emulsifying ammonium hydrogen phosphate/ammonium phosphate to obtain a precursor;
The specific contents are as follows:
preparing purified lignin into a solution with the concentration of 3-10wt%; the mass ratio of the purified lignin solution to the ammonium hydrogen phosphate/ammonium phosphate is 5-20:1, and further can be 5:1, 10:1, 15:1 and 20:1; the emulsifying oil is olive oil and/or glycerol; the lignin and the ammonium hydrogen phosphate/ammonium phosphate are blended to obtain a treatment liquid, and then the treatment liquid is dripped into olive oil and/or glycerin to form a spherical oil water micro-dripping (W/O) emulsion through dispersion. The mass ratio of the treatment fluid to the olive oil and/or glycerin is 1:50. In the treatment process, after maintaining the water bath at 70-90 ℃ for 500-800 r/min for 1-3 h, centrifuging to remove olive oil/glycerol, washing the generated dark precipitate with hexane for 3 times, and drying at room temperature to obtain lignin precursor.
S3, solidifying the precursor and the epoxy resin, and carbonizing to obtain a hard carbon material;
The specific contents are as follows:
The precursor and the epoxy resin are dripped into an alcohol solution according to the mass ratio of 3-7:7-3 (further can be 3:7,5:5 and 7:3), stirred for 1h at 30 ℃, and then cured.
Curing: 130-170 ℃ and 18-40 h;
Carbonizing: 1200-1600 ℃, 0.5-3 h, 0.5-3 ℃/min. The carbonization temperature may further be 1200, 1400, 1600 ℃, more preferably 1400 ℃.
The lignin can cure the epoxy resin without any curing agent, so that an interpenetrating polymer network is formed, the formed carbon material has a stable structure, the number of the near-layer ordered graphite layers is increased, the interlayer spacing is large, and the sodium storage is facilitated. In the calcination process, because (NH 4)2HPO4 is decomposed at 209 ℃ (NH 3+ P2O5+ H2 O is obtained by decomposition) and lignin is continuously pyrolyzed at 340 ℃, pores are generated in each hard carbon microsphere formed by lignin microdroplets, and in-situ hetero atoms of N and P elements in a formed carbon matrix are doped with an NH 4 + group or a generated P-O-C bond can promote dehydration reaction of-OH, -OCH 3 and H atoms on aromatic rings to form larger graphite-like crystals and target hard carbon.
The invention adopts the technical mechanism and has the beneficial effects that:
The invention uses lignin biomass as a carbon source, and synthesizes N, P co-doped hard carbon microspheres with controllable microstructure and morphology by an ammonium hydrogen phosphate/ammonium phosphate mediated emulsion-solvent evaporation method. Lignin cures the epoxy resin without any curing agent, and an Interpenetrating Polymer Network (IPN) can be formed between the lignin and the epoxy resin; with the increase of the mass ratio of the epoxy resin to the lignin, on one hand, the graphitization degree is improved, the interlayer distance is reduced, and on the other hand, the lignin content can influence the crosslinking degree of the epoxy resin, and after balancing the factors, the carbon material with high reversible capacity is obtained. Compared with the independent lignin precursor, the structure of the IPN is more favorable for forming larger interlayer distance, sodium ions are easier to interpenetrate between the layers, graphite microcrystals and disordered regions coexist in a harmonious mode, the average interlayer distance is increased compared with that of original graphite, and the average interlayer distance is increased due to the fact that normal-position N, P atoms are co-doped to increase local conductivity, moderate macropores exist, so that the capacity of a platform region of a sodium battery is improved, and the electrochemical performance is remarkably improved.
Drawings
FIG. 1 is an XRD pattern of a hard carbon material prepared in example 1 of the present invention;
FIG. 2 is a scanning electron microscope image of the hard carbon material prepared in example 1 of the present invention;
fig. 3 is a charge-discharge graph of the sodium ion battery prepared in example 1 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions of the embodiments of the present invention will be clearly and completely described below. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
1. Examples
Example 1
(1) Purification of industrial lignin
Mixing sodium lignin sulfonate with an organic acid mixed solution according to a mass ratio of 1:3 for heat treatment, wherein the organic acid mixed solution is prepared from 40% of acetic acid and propionic acid according to a volume ratio of 1:1. And filtering while the lignin is hot, and then adding water into the filtrate for dilution and then carrying out solid-liquid separation to obtain the pretreated lignin.
Pulverizing and grinding the pretreated lignin, mixing with mixed acid according to a mass ratio of 1:3, heating to 75 ℃, maintaining at 1h, cooling, and suction filtering. Repeating the above pickling steps until the 3 rd pickling is completed. And (3) washing with acid, rinsing with hot water for multiple times until the pH value of the filtrate is 6-7, and finally drying the sample at 120 ℃ for 10 h to obtain a lignin sample. Wherein the mixed acid liquid is prepared from hydrochloric acid, sulfuric acid and nitric acid with the concentration of 2 mol/L, and the volume ratio of the mixed acid liquid is V (HCl): v (H 2SO4)：V(HNO3) =2:2:1, mixed acid concentration V (acid): V (water) =1:1. The obtained lignin sample with a certain amount is dissolved in a mixed solution composed of acetone and deionized water, the mixed solution is stirred for 1h, then the upper solution is collected, the vacuum drying is carried out at 80 ℃ for 10 h, the purified lignin is obtained, wherein the mass ratio of the lignin sample to the mixed solution is 1:6, the mixed solution is prepared from deionized water and acetone, and the volume ratio of the mixed solution is 1:5.
(2) Preparation of hard carbon negative electrode material
Preparing a lignin aqueous solution with the concentration of 5% from the purified lignin obtained in the step (1), mixing the lignin aqueous solution with ammonium hydrogen phosphate according to a mass ratio of 5:1 to obtain a mixed solution, wherein the mass ratio of the mixed solution to the olive oil is 1:50, and dripping the mixed solution into the olive oil, wherein the water bath temperature is kept at about 80 ℃, and the stirring speed is kept at 600 r/min. After stirring for two hours, the olive oil was removed by centrifugation, and the resulting dark precipitate was washed 3 times with hexane and dried at room temperature to give the initial precursor.
The initial precursor and epoxy resin were then dissolved in 75% volume fraction alcohol solution at a mass ratio of 5:5 and stirred at 30 ℃ for 1 h. The slurry was then cured 24h at 150 ℃ and further carbonized 1h at 1400 ℃ at a heating rate of 2 ℃/min to yield a carbon material.
Example 2
The difference between this example and example 1 is that (1) the mass ratio of lignin aqueous solution to ammonium hydrogen phosphate is 20:1; (2) The mass ratio of the initial precursor to the epoxy resin is 7:3, and the carbonization temperature is 1200 ℃.
Example 3
The difference between this example and example 1 is that (1) the mass ratio of lignin aqueous solution to ammonium hydrogen phosphate is 10:1; (2) The mass ratio of the initial precursor to the epoxy resin is 3:7, and the carbonization temperature is 1600 ℃.
2. Comparative example
Comparative example 1
The difference between this comparative example and example 1 is that (2) the obtained purified lignin is prepared into a lignin aqueous solution of 5% and mixed with ammonium hydrogen phosphate in a mass ratio of 5:1, wherein the mass ratio of the mixed solution to olive oil is 1:50, and the mixed solution is dropped into olive oil, wherein the water bath temperature is kept at about 80 ℃, and the stirring speed is kept at 600 r/min. After stirring for two hours, the olive oil is removed by centrifugation, the generated dark precipitate is washed by hexane for 3 times, the original precursor is obtained by drying at room temperature, and then the carbon material is obtained by further carbonization of 1 h at 1400 ℃ at a heating rate of 2 ℃/min.
Comparative example 2
This comparative example differs from example 1 in that in (2), the purified lignin and the epoxy resin were dissolved in a mass ratio of 5:5 in a 75% volume fraction of an alcohol solution and stirred at 30℃for 1h. The slurry was then cured 24 h at 150 ℃ and further carbonized 1h at 1400 ℃ at a heating rate of 2 ℃/min to obtain a carbon material.
Comparative example 3
This comparative example is different from example 1 in that (2) the purified lignin was further carbonized at 1400 ℃ for 1 h at a heating rate of 2 ℃/min to obtain a carbon material.
3. Test examples
Test example 1:
The hard carbon materials obtained in examples 1 to 3 and comparative examples 1 to 3 were subjected to the relevant performance test, and the test results obtained are shown in Table 1.
The hard carbon materials obtained in examples 1 to 3 and comparative examples 1 to 3 were used to assemble sodium batteries for electrochemical performance testing; the test conditions were current density of 0.1A/g and voltage range of 0 to 3V, and the multiplying power test was performed with 0.1C and 0.2C, and the test results obtained are shown in Table 2.
XRD and SEM tests were conducted on the hard carbon material prepared in example 1, and the results are shown in FIGS. 1 and 2, and charge and discharge tests were conducted on the assembled sodium battery, and the results are shown in FIG. 3.
TABLE 1 hard carbon Material Properties
Table 2 electrochemical performance of sodium ion batteries
From the data in tables 1 and 2, it can be seen that:
The hard carbon anode material prepared in the embodiment 1 is doped with N and P and is compounded with epoxy resin, so that the hard carbon nano-pore microsphere with the co-doped N and P and the IPN structure is formed, the formation of a larger interlayer distance is facilitated, and the interlayer distance d 002 = 0.386nm is the largest; the local conductivity due to the doping of the heteroatoms is stronger, and increasing the amount of NH 4)2HPO4 added in the solution is greatly advantageous for increasing the coulombic efficiency of the hard carbon negative electrode material, so that the sample of example 1 has the highest ice=97.3%, its specific surface area S BET=14.2 m2/g and pore volume V P=0.0270 cm3/g, which are also higher than those of examples 2-3 and comparative examples 1-3.
The carbonization temperature implemented in example 3 was 1600 ℃, the defect sites and interlayer distance of the sample were reduced, leading to limited Na + diffusion, and the rate performance and capacity were reduced, i.e. the defect sites were more conducive to rapid transport of Na +, resulting in high capacity retention at a higher rate than graphite flake. However, a low carbonization temperature does not produce a high capacity, and the carbonization temperature performed in example 2 is 1200 ℃, and the electron conductivity due to insufficient carbonization is low, and even a good rate capacity cannot be maintained.
Comparative example 3 sample, which was not N, P doped and compounded with epoxy resin, had minimal interlayer spacing, specific surface area and pore volume compared to the other samples, resulting in fewer sodium storage sites, limited Na + diffusion capacity, and ultimately poor cell performance.
The good performance is attributed to the stable structure of the prepared carbon material, large interlayer spacing, and the addition of the unique crosslinked network from single precursor to combined precursor, short-range ordered graphite layer, which is favorable for carrying Na +. In particular, it is possible to exhibit excellent rate performance and cycle stability due to optimal physicochemical characteristics such as S BET value, porous structure facilitating mass transfer of electrolyte, and local conductivity associated with graphite-like grain size and N, P co-doping.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (8)
1. The preparation method of the hard carbon anode material for the sodium ion battery is characterized by comprising the following steps of:
s1, treating a lignin raw material to obtain purified lignin;
S2, in a solvent system, purifying lignin and ammonium phosphate/ammonium hydrogen phosphate, and emulsifying to obtain a precursor;
and S3, curing and carbonizing the precursor and the epoxy resin to obtain the hard carbon material.
2. The method for producing a hard carbon negative electrode material for sodium ion battery according to claim 1, wherein the treatment in S1 comprises heat treatment, acid washing, and S1 comprises at least one of features (S1-1) to (S1-2):
(S1-1) heat treatment: carrying out heat treatment on lignin raw materials and organic acid to obtain a pretreated substance;
(S1-2) acid washing: heating and rinsing the pretreated matter and the mixed acid liquor to obtain an acid-washed matter; and dissolving and drying the acid washing substance to obtain the purified lignin.
3. The method for producing a hard carbon negative electrode material for sodium-ion batteries according to claim 2, wherein (S1-1) comprises at least one of features (S1-1-1) to (S1-1-3):
(S1-1-1) the mass ratio of the lignin raw material to the organic acid is 1:2-6;
(S1-1-2) the organic acid comprises acetic acid and propionic acid, and the volume ratio of the acetic acid to the propionic acid is 1:1;
(S1-1-3) the lignin raw material comprises at least one of sodium lignin sulfonate and sodium lignin sulfate.
4. The method for producing a hard carbon negative electrode material for sodium-ion batteries according to claim 2, wherein (S1-2) includes at least one of features (S1-2-1) to (S1-2-3):
(S1-2-1) the mixed acid solution comprises hydrochloric acid, sulfuric acid and nitric acid;
(S1-2-2) the mass ratio of the pretreated matter to the mixed acid liquid is 1:1-5;
(S1-2-3) heating: 60-85 ℃ and 0.5-2 h.
5. The method for producing a hard carbon negative electrode material for sodium-ion battery according to claim 1, wherein S3 includes at least one of features (S3-1) to (S3-3):
(S3-1) the mass ratio of the precursor to the epoxy resin is 3-7:7-3;
(S3-2) curing: 130-170 ℃ and 18-40 h;
(S3-3) carbonization: 1200-1600 ℃, 0.5-3 h, 0.5-3 ℃/min.
6. The method for producing a hard carbon negative electrode material for a sodium ion battery according to claim 5, wherein (S3-3) comprises the following features (S3-3-1):
(S3-3-1) carbonization temperature was selected to be 1200, 1400, or 1600 ℃.
7. The method for producing a hard carbon negative electrode material for sodium-ion battery according to any one of claims 1 to 6, wherein S2 includes at least one of features (S2-1) to (S2-4):
(S2-1) preparing purified lignin into a solution, wherein the concentration of the solution is 3-10wt%;
(S2-2) the mass ratio of the purified lignin solution to ammonium hydrogen phosphate/ammonium phosphate is 5-20:1;
(S2-3) the emulsifying oil is olive oil and/or glycerol;
(S2-4) emulsification: and maintaining the water bath at 70-90 ℃ for 1-3 hours at 500-800 r/min.
8. A hard carbon negative electrode material obtained by the production method according to any one of claims 1 to 7.
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