CN118270764A - Hard carbon anode material and preparation method and application thereof - Google Patents
Hard carbon anode material and preparation method and application thereof Download PDFInfo
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- CN118270764A CN118270764A CN202410542593.8A CN202410542593A CN118270764A CN 118270764 A CN118270764 A CN 118270764A CN 202410542593 A CN202410542593 A CN 202410542593A CN 118270764 A CN118270764 A CN 118270764A
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- 229910021385 hard carbon Inorganic materials 0.000 title claims abstract description 104
- 239000010405 anode material Substances 0.000 title claims abstract description 81
- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- 239000002253 acid Substances 0.000 claims abstract description 59
- 239000000463 material Substances 0.000 claims abstract description 52
- UKLNMMHNWFDKNT-UHFFFAOYSA-M sodium chlorite Chemical compound [Na+].[O-]Cl=O UKLNMMHNWFDKNT-UHFFFAOYSA-M 0.000 claims abstract description 46
- 229960002218 sodium chlorite Drugs 0.000 claims abstract description 46
- 239000002023 wood Substances 0.000 claims abstract description 30
- 238000003763 carbonization Methods 0.000 claims abstract description 28
- 230000003647 oxidation Effects 0.000 claims abstract description 21
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 21
- 238000002791 soaking Methods 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 46
- 238000010438 heat treatment Methods 0.000 claims description 43
- 239000012298 atmosphere Substances 0.000 claims description 33
- 239000007773 negative electrode material Substances 0.000 claims description 20
- 241000124033 Salix Species 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 18
- 238000004321 preservation Methods 0.000 claims description 9
- DSSYKIVIOFKYAU-XCBNKYQSSA-N (R)-camphor Chemical compound C1C[C@@]2(C)C(=O)C[C@@H]1C2(C)C DSSYKIVIOFKYAU-XCBNKYQSSA-N 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 244000082946 Tarchonanthus camphoratus Species 0.000 claims description 6
- 235000005701 Tarchonanthus camphoratus Nutrition 0.000 claims description 6
- 235000018185 Betula X alpestris Nutrition 0.000 claims description 5
- 235000018212 Betula X uliginosa Nutrition 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 235000008331 Pinus X rigitaeda Nutrition 0.000 claims description 5
- 241000018646 Pinus brutia Species 0.000 claims description 5
- 235000011613 Pinus brutia Nutrition 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- 230000001681 protective effect Effects 0.000 claims description 5
- 240000001606 Adenanthera pavonina Species 0.000 claims description 4
- 235000011470 Adenanthera pavonina Nutrition 0.000 claims description 4
- 235000011201 Ginkgo Nutrition 0.000 claims description 4
- 244000194101 Ginkgo biloba Species 0.000 claims description 4
- 235000008100 Ginkgo biloba Nutrition 0.000 claims description 4
- 240000007049 Juglans regia Species 0.000 claims description 4
- 235000009496 Juglans regia Nutrition 0.000 claims description 4
- 235000016976 Quercus macrolepis Nutrition 0.000 claims description 4
- 235000020234 walnut Nutrition 0.000 claims description 4
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 claims description 3
- 244000055346 Paulownia Species 0.000 claims description 3
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- 241001106462 Ulmus Species 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 229920000137 polyphosphoric acid Polymers 0.000 claims description 3
- 241000750718 Pterocarpus santalinus Species 0.000 claims description 2
- 230000000630 rising effect Effects 0.000 claims description 2
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- 244000301850 Cupressus sempervirens Species 0.000 claims 1
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 5
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Abstract
The invention relates to the technical field of batteries, in particular to a hard carbon anode material and a preparation method and application thereof. The preparation method of the hard carbon anode material comprises the following steps: placing wood in an acid solution of sodium chlorite for soaking treatment to obtain a treated material; and sequentially carrying out oxidation treatment and carbonization treatment on the treatment material to obtain the hard carbon anode material. According to the invention, natural wood is used as a carbon source, and the acid solution of sodium chlorite is used for carrying out chemical treatment on the wood, so that impurities such as lignin, metal and the like can be removed, and ash content of the wood is obviously reduced; the low-temperature oxidation treatment can obviously improve the carbonization yield of the hard carbon anode material derived from the wood, thereby reducing the cost of the hard carbon; and then carrying out carbonization treatment at a proper temperature to obtain the hard carbon anode material. The method is simple and easy to implement, and the obtained anode material has excellent capacity and coulombic efficiency.
Description
Technical Field
The invention relates to the technical field of batteries, in particular to a hard carbon anode material and a preparation method and application thereof.
Background
With the development of new energy technology, especially the rapid expansion of renewable energy power generation of solar energy, wind energy and the like, the demand for energy storage batteries is more and more urgent. Sodium ion batteries are considered as novel batteries which are most suitable for large-scale energy storage, and are expected to relieve the problems of limited energy storage development and the like caused by lithium resource shortage and maldistribution.
Compared with a lithium ion battery, the radius of sodium ions is more than 35% larger than that of lithium ions, and the aperture and the interlayer spacing of a graphite negative electrode in the main stream of the lithium ion battery are smaller, so that the requirement of the negative electrode of the sodium ion battery cannot be met, and therefore, a hard carbon negative electrode is mainly used in the main stream of the sodium ion battery. The preparation process of the hard carbon material in the prior art is complex, and the electrochemical performance of the hard carbon material is not ideal.
In view of this, the present invention has been made.
Disclosure of Invention
The invention aims to provide a preparation method of a hard carbon anode material, which is simple and feasible, and the obtained anode material has the characteristics of high capacity and high coulombic efficiency.
The invention also aims to provide the hard carbon anode material prepared by the preparation method of the hard carbon anode material.
Another object of the present invention is to provide a negative electrode sheet.
Another object of the present invention is to provide a battery.
In order to achieve the above object of the present invention, the following technical solutions are specifically adopted:
The preparation method of the hard carbon anode material comprises the following steps:
placing wood in an acid solution of sodium chlorite for soaking treatment to obtain a treated material;
And sequentially carrying out oxidation treatment and carbonization treatment on the treatment material to obtain the hard carbon anode material.
In some embodiments, the wood comprises at least one of elm, willow, oak, walnut, birch, camphor wood, nanmu, boxwood, paulownia, red sandalwood, rosewood, mahogany, chromowood, pine, cypress, fir, ginkgo, teak, and red sandalwood.
In some embodiments, the wood has a length of 3 to 5cm.
In some embodiments, the concentration of sodium chlorite in the acid solution of sodium chlorite is 0.1-6 mol/L.
In some embodiments, the acid concentration in the acid solution of sodium chlorite is 0.1-3 mol/L.
In some embodiments, the acid solution of sodium chlorite comprises at least one of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, hydrobromic acid, and polyphosphoric acid.
In some embodiments, the soaking treatment is for 8 to 15 hours.
In some embodiments, the soaking treatment is followed by a drying treatment.
In some embodiments, the temperature of the drying process after the soaking process is 70 to 110 ℃.
In some embodiments, the temperature of the oxidation treatment is 200-300 ℃ and the time of the oxidation treatment is 1-12 h.
In some embodiments, the atmosphere of the oxidizing treatment is an air atmosphere.
In some embodiments, the oxidation treatment has a ramp rate of 1 to 5 ℃/min.
In some embodiments, the heat preservation temperature of the carbonization treatment is 1350-1600 ℃, and the heat preservation time of the carbonization treatment is 2-5 h.
In some embodiments, the atmosphere of the carbonization treatment is a protective gas.
In some embodiments, the carbonization treatment has a heating rate of 1 to 20 ℃/min.
In some embodiments, the protective gas comprises at least one of Ar, he, N 2、H2、NH3, and CO 2.
In some embodiments, after the carbonization treatment, the method further comprises: the mass was cooled to room temperature.
The hard carbon anode material prepared by the preparation method of the hard carbon anode material is prepared.
In some embodiments, the hard carbon anode material has a capacity of greater than 330mAh/g and a coulombic efficiency of greater than 91.5% at a current density of 30 mA/g.
The negative electrode plate comprises the hard carbon negative electrode material prepared by the preparation method of the hard carbon negative electrode material.
A battery comprises the negative plate.
Compared with the prior art, the invention has the beneficial effects that:
(1) According to the invention, natural wood is used as a carbon source, and the acid solution of sodium chlorite is used for carrying out chemical treatment on the wood, so that impurities such as lignin, metal and the like can be removed, and ash content of the wood is obviously reduced; the carbonization yield (100% -200%) of the hard carbon anode material derived from the wood can be obviously improved by low-temperature oxidation treatment, so that the hard carbon cost is reduced; and then carrying out carbonization treatment at a proper temperature to obtain the hard carbon anode material. The method is simple and easy to implement, and the obtained anode material has excellent capacity and coulombic efficiency.
(2) The battery has the characteristics of high capacity and high coulombic efficiency.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are needed in the description of the embodiments or the prior art will be briefly described, and it is obvious that the drawings in the description below are some embodiments of the present invention, and other drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.
FIG. 1 is an X-ray diffraction pattern (XRD) of a hard carbon negative electrode material in example 1 of the present invention;
Fig. 2 is an electrochemical performance chart of a battery corresponding to the hard carbon negative electrode material in example 1 of the present invention.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention. 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.
According to one aspect of the invention, the invention relates to a preparation method of a hard carbon anode material, which comprises the following steps:
placing wood in an acid solution of sodium chlorite for soaking treatment to obtain a treated material;
And sequentially carrying out oxidation treatment and carbonization treatment on the treatment material to obtain the hard carbon anode material.
According to the invention, natural wood is used as a carbon source, and an acid solution of sodium chlorite is adopted to chemically treat the wood, so that impurities such as lignin and metal can be removed, and ash content of the wood is obviously reduced; and then the low-temperature oxidation treatment is carried out, so that the carbonization yield (100% -200%) of the hard carbon anode material derived from the wood can be obviously improved, and the hard carbon cost is reduced. And then the hard carbon anode material is obtained through proper temperature carbonization treatment, and the anode material has excellent capacity and coulombic efficiency.
In one embodiment, the wood comprises at least one of elm, willow, oak, walnut, birch, camphorwood, nanmu, buxus, paulownia, pterocarpus santalinus, rosewood, mahogany, chromowood, pine, cypress, sequoia, ginkgo, teak, and red sandalwood. The invention adopts the natural wood, has low cost and wide sources.
In one embodiment, the length of the wood is 3 to 5cm, such as 3cm, 3.5cm, 4cm, 5cm, etc. The length of the wood in each embodiment of the invention is 3-5 cm.
In one embodiment, the wood may be selected from any one or a combination of at least two of the above-mentioned woods, for example, a combination of elm and willow, a combination of fir and ginkgo, a combination of camphor wood, phyllostachys pubescens and boxwood, a combination of walnut, birch, camphor wood and cypress, and the like.
In one embodiment, the concentration of sodium chlorite in the acid solution of sodium chlorite is 0.1-6 mol/L. In one embodiment, the concentration of sodium chlorite includes, but is not limited to, 0.1, 0.5, 1,2,3,4, 5, or 6 mole/liter, etc. In one embodiment, the acid concentration in the sodium chlorite acid solution is 0.1-3 mol/L, including but not limited to 0.1mol/L, 0.5mol/L, 1mol/L, 1.5mol/L, 2mol/L, 3mol/L, etc. In the acid solution of sodium chlorite, the acid comprises at least one of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, hydrobromic acid and polyphosphoric acid. The method adopts the acid solution of sodium chlorite with proper concentration to treat wood so as to remove lignin, metal and other impurities better.
In one embodiment, the soaking treatment is performed for 8-15 hours, including but not limited to 8 hours, 9 hours, 10 hours, 11 hours, 12 hours, 13 hours, 15 hours, etc. The invention ensures the effective removal of lignin, metal and other impurities through proper soaking treatment time.
In one embodiment, the soaking treatment is followed by a drying treatment. The drying treatment after the soaking treatment is performed at a temperature of 70-110 ℃, including, but not limited to, 70 ℃, 75 ℃, 80 ℃, 85 ℃, 90 ℃, 95 ℃, 100 ℃, 105 ℃, 110 ℃, or the like. The moisture in the treated material is removed by a drying process.
In one embodiment, the oxidation treatment is performed at a soak temperature of 200 to 300℃including, but not limited to, 200℃210℃220℃230℃240℃250℃260℃270℃300℃and the like. The heat preservation time of the oxidation treatment is 1-12 h, including but not limited to 1h, 2h, 3h, 5h, 6h, 7h, 8h, 9h or 10h, etc. In one embodiment, the atmosphere of the oxidation treatment is an air atmosphere; the temperature rising rate of the oxidation treatment is 1-5 ℃/min, such as 1 ℃/min, 2 ℃/min, 3 ℃/min, 4 ℃/min or 5 ℃/min, etc. The invention adopts proper oxidation treatment temperature and time, thereby ensuring high conversion rate of the subsequent carbonization treatment.
In one embodiment, the carbonization treatment is performed at a soak temperature of 1350-1600 ℃, including, but not limited to 1350 ℃, 1370 ℃, 1400 ℃, 1450 ℃, 1500 ℃, 1550 ℃, 1580 ℃, 1600 ℃, and the like. The heat preservation time of the carbonization treatment is 2-5 h, including but not limited to 2h, 3h, 4h or 5h, etc. The atmosphere of the carbonization treatment is a protective gas, which in one embodiment includes at least one of Ar, he, N 2、H2、NH3, and CO 2; the heating rate of the carbonization treatment is 1-20 ℃/min, such as1 ℃/min, 2 ℃/min, 5 ℃/min, 10 ℃/min or 20 ℃/min, etc. The invention adopts proper heat preservation temperature and time matching of carbonization treatment, thereby ensuring high capacity and high initial efficiency of the hard carbon cathode material.
In one embodiment, after the carbonization treatment, the method further comprises: the mass was cooled to room temperature.
According to another aspect of the invention, the invention also relates to the hard carbon anode material prepared by the preparation method of the hard carbon anode material. The hard carbon anode material has the characteristics of high capacity and high coulomb efficiency, the capacity is more than 330mAh/g under the current density of 30mA/g, and the coulomb efficiency is more than 91.5%.
According to another aspect of the invention, the invention also relates to a negative electrode sheet, which comprises the hard carbon negative electrode material prepared by the preparation method of the hard carbon negative electrode material.
In one embodiment, the negative electrode sheet includes a negative electrode current collector and a negative electrode material layer disposed on at least one side surface of the negative electrode current collector; the negative electrode material layer contains the hard carbon negative electrode material described above.
According to another aspect of the invention, the invention also relates to a battery, comprising the negative plate.
The battery comprises the negative plate, the positive plate, the diaphragm and the electrolyte. The battery of the invention has high capacity and excellent cycle performance.
The following is a further explanation in connection with specific examples, comparative examples.
Example 1
The preparation method of the hard carbon anode material comprises the following steps:
1000g of dried elm was placed in 500mL of an acid solution (0.5 mol/L) of sodium chlorite (1 mol/L) as a hydrochloric acid solution and dried at 100℃for 12 hours to obtain a treated material.
And (3) placing the treatment material in a tubular furnace in an air atmosphere, heating to 240 ℃ at 2 ℃/min, preserving heat for 6 hours, changing into an N 2 atmosphere, and heating to 1400 ℃ at 2 ℃/min, preserving heat for 3 hours. Cooling to room temperature to obtain the hard carbon anode material.
The XRD pattern of the hard carbon negative electrode material in this example is shown in fig. 1.
Example 2
The preparation method of the hard carbon anode material comprises the following steps:
1000g of dried willow is placed in 500mL of sodium chlorite (1 mol/L) acid solution (0.5 mol/L) for standing for 12h, the acid solution is hydrochloric acid solution, and the treated material is obtained by drying at 100 ℃.
And (3) placing the treatment material in a tubular furnace in an air atmosphere, heating to 250 ℃ at 2 ℃/min, preserving heat for 4 hours, changing into an N 2 atmosphere, and heating to 1400 ℃ at 2.5 ℃/min, and preserving heat for 3 hours. Cooling to room temperature to obtain the hard carbon anode material.
Example 3
The preparation method of the hard carbon anode material comprises the following steps:
1000g of dried oak wood was placed in 500mL of an acid solution (0.5 mol/L) of sodium chlorite (1 mol/L) as a hydrochloric acid solution and dried at 100℃for 12 hours to obtain a treated material.
And (3) placing the treatment material in a tubular furnace in an air atmosphere, heating to 250 ℃ at 2 ℃/min, preserving heat for 4 hours, changing into an N 2 atmosphere, and heating to 1400 ℃ at 2.5 ℃/min, and preserving heat for 3 hours. Cooling to room temperature to obtain the hard carbon anode material.
Example 4
The preparation method of the hard carbon anode material comprises the following steps:
1000g of dried birch was placed in 500mL of an acid solution (0.5 mol/L) of sodium chlorite (1 mol/L) as a hydrochloric acid solution and dried at 100℃for 12 hours to obtain a treated material.
And (3) placing the treatment material in a tubular furnace in an air atmosphere, heating to 250 ℃ at 2 ℃/min, preserving heat for 4 hours, changing into an N 2 atmosphere, and heating to 1400 ℃ at 2.5 ℃/min, and preserving heat for 3 hours. Cooling to room temperature to obtain the hard carbon anode material.
Example 5
The preparation method of the hard carbon anode material comprises the following steps:
1000g of dried camphorwood was placed in 500mL of an acid solution (0.5 mol/L) of sodium chlorite (1 mol/L) as a hydrochloric acid solution and dried at 100℃for 12 hours to obtain a treated material.
And (3) placing the treatment material in a tubular furnace in an air atmosphere, heating to 250 ℃ at 2 ℃/min, preserving heat for 4 hours, changing into an N 2 atmosphere, and heating to 1400 ℃ at 2.5 ℃/min, and preserving heat for 3 hours. Cooling to room temperature to obtain the hard carbon anode material.
Example 6
The preparation method of the hard carbon anode material comprises the following steps:
1000g of dried nanmu was placed in 500mL of an acid solution (0.5 mol/L) of sodium chlorite (1 mol/L) as a hydrochloric acid solution and dried at 100℃for 12 hours to obtain a treated material.
Placing the treated material in a tubular furnace in an air atmosphere, heating to 250 ℃ at 2 ℃/min, preserving heat for 4 hours, changing into an N 2 atmosphere, heating to 1400 ℃ at 2.5 ℃/min, and preserving heat for 3 hours. Cooling to room temperature to obtain the hard carbon anode material.
Example 7
The preparation method of the hard carbon anode material comprises the following steps:
1000g of dried pine wood was placed in 500mL of an acid solution (0.5 mol/L) of sodium chlorite (1 mol/L) as a hydrochloric acid solution and dried at 100℃for 12 hours to obtain a treated material.
And (3) placing the treatment material in a tubular furnace in an air atmosphere, heating to 250 ℃ at 2 ℃/min, preserving heat for 4 hours, changing into an N 2 atmosphere, and heating to 1400 ℃ at 2.5 ℃/min, and preserving heat for 3 hours. Cooling to room temperature to obtain the hard carbon anode material.
Example 8
The preparation method of the hard carbon anode material comprises the following steps:
1000g of dried cypress was placed in 500mL of an acid solution (0.5 mol/L) of sodium chlorite (1 mol/L) as a hydrochloric acid solution and dried at 100℃for 12 hours to obtain a treated material.
Placing the treated material in a tubular furnace in an air atmosphere, heating to 250 ℃ at 2 ℃/min, preserving heat for 4 hours, changing into an N 2 atmosphere, heating to 1400 ℃ at 2.5 ℃/min, and preserving heat for 3 hours. Cooling to room temperature to obtain the hard carbon anode material.
Example 9
The preparation method of the hard carbon anode material comprises the following steps:
1000g of dried cypress was placed in 500mL of an acid solution (0.5 mol/L) of sodium chlorite (2 mol/L) as a hydrochloric acid solution and dried at 100℃for 12 hours to obtain a treated material.
And (3) placing the treatment material in a tubular furnace in an air atmosphere, heating to 250 ℃ at 2 ℃/min, preserving heat for 4 hours, changing into an N 2 atmosphere, and heating to 1400 ℃ at 2.5 ℃/min, and preserving heat for 3 hours. Cooling to room temperature to obtain the hard carbon anode material.
Example 10
The preparation method of the hard carbon anode material comprises the following steps:
1000g of dried cypress was placed in 500mL of sodium chlorite (3 mol/L) in an acid solution (0.5 mol/L) as hydrochloric acid solution and dried at 100℃for 12 hours. Placing the treated material in a tubular furnace in an air atmosphere, heating to 250 ℃ at 2 ℃/min, preserving heat for 4 hours, changing into an N 2 atmosphere, heating to 1400 ℃ at 2.5 ℃/min, and preserving heat for 3 hours. Cooling to room temperature to obtain the hard carbon anode material.
Example 11
The preparation method of the hard carbon anode material comprises the following steps:
1000g of dried cypress was placed in 500mL of an acid solution (0.5 mol/L) of sodium chlorite (4 mol/L) as a hydrochloric acid solution and dried at 100℃for 12 hours to obtain a treated material.
And (3) placing the treatment material in a tubular furnace in an air atmosphere, heating to 250 ℃ at 2 ℃/min, preserving heat for 4 hours, changing into an N 2 atmosphere, and heating to 1400 ℃ at 2.5 ℃/min, and preserving heat for 3 hours. Cooling to room temperature to obtain the hard carbon anode material.
Example 12
The preparation method of the hard carbon anode material comprises the following steps:
1000g of dried willow is placed in 500mL of sodium chlorite (2 mol/L) acid solution (1 mol/L) for standing for 8h, the acid solution is hydrochloric acid solution, and the treated material is obtained by drying at 100 ℃.
And (3) placing the treatment material in a tubular furnace in an air atmosphere, heating to 250 ℃ at 5 ℃/min, preserving heat for 6 hours, changing into an N 2 atmosphere, and heating to 1500 ℃ at 2.5 ℃/min, and preserving heat for 3 hours. Cooling to room temperature to obtain the hard carbon anode material.
Example 13
The preparation method of the hard carbon anode material comprises the following steps:
1000g of dried willow is placed in 500mL of sodium chlorite (2 mol/L) acid solution (0.5 mol/L) for standing for 8h, the acid solution is hydrochloric acid solution, and the treated material is obtained by drying at 100 ℃.
The treatment material is placed in a tubular furnace in air atmosphere, the temperature is raised to 250 ℃ at 2.5 ℃/min, the temperature is kept for 3 hours, the temperature is changed into N 2 atmosphere, and the temperature is raised to 1450 ℃ at 1.5 ℃/min, and the temperature is kept for 3 hours. Cooling to room temperature to obtain the hard carbon anode material.
Example 14
The preparation method of the hard carbon anode material comprises the following steps:
1000g of dried willow is placed in 500mL of sodium chlorite (2 mol/L) acid solution (0.5 mol/L) for standing for 8h, the acid solution is hydrochloric acid solution, and the treated material is obtained by drying at 100 ℃.
And (3) placing the treatment material in a tubular furnace in an air atmosphere, heating to 260 ℃ at 3 ℃/min, preserving heat for 3 hours, changing into an N 2 atmosphere, and heating to 1400 ℃ at 2.5 ℃/min, and preserving heat for 3 hours. Cooling to room temperature to obtain the hard carbon anode material.
Example 15
The preparation method of the hard carbon anode material comprises the following steps:
1000g of dried willow is placed in 500mL of sodium chlorite (2 mol/L) acid solution (0.5 mol/L) for standing for 8h, the acid solution is hydrochloric acid solution, and the treated material is obtained by drying at 100 ℃.
Placing the treated material in a tubular furnace in an air atmosphere, heating to 280 ℃ at 3 ℃/min, preserving heat for 3 hours, changing into an N 2 atmosphere, heating to 1400 ℃ at 2.5 ℃/min, and preserving heat for 3 hours. Cooling to room temperature to obtain the hard carbon anode material.
Example 16
The preparation method of the hard carbon anode material comprises the following steps:
1000g of dried willow is placed in 500mL of sodium chlorite (2 mol/L) acid solution (0.5 mol/L) for standing for 8h, the acid solution is hydrochloric acid solution, and the treated material is obtained by drying at 100 ℃.
And (3) placing the treatment material in a tubular furnace in an air atmosphere, heating to 300 ℃ at 3 ℃/min, preserving heat for 2 hours, changing into an N 2 atmosphere, and heating to 1400 ℃ at 2.5 ℃/min, and preserving heat for 3 hours. Cooling to room temperature to obtain the hard carbon anode material.
Example 17
A hard carbon negative electrode material and a preparation method thereof comprise the following steps:
1000g of dried willow is placed in 500mL of sodium chlorite (2 mol/L) acid solution (0.5 mol/L) for standing for 8h, the acid solution is hydrochloric acid solution, and the treated material is obtained by drying at 100 ℃.
Placing the treated material in a tubular furnace in an air atmosphere, heating to 250 ℃ at 5 ℃/min, preserving heat for 6 hours, changing into an N 2 atmosphere, heating to 1500 ℃ at 2.5 ℃/min, and preserving heat for 3 hours. Cooling to room temperature to obtain the hard carbon anode material.
Example 18
The preparation method of the hard carbon anode material comprises the following steps:
1000g of dried willow is placed in 500mL of sodium chlorite (2 mol/L) acid solution (0.5 mol/L) for standing for 8h, the acid solution is hydrochloric acid solution, and the treated material is obtained by drying at 100 ℃.
And (3) placing the treatment material in a tubular furnace in an air atmosphere, heating to 250 ℃ at 5 ℃/min, preserving heat for 6 hours, changing into an N 2 atmosphere, and heating to 1500 ℃ at 1.5 ℃/min, and preserving heat for 3 hours. Cooling to room temperature to obtain the hard carbon anode material.
Example 19
The preparation method of the hard carbon anode material comprises the following steps:
1000g of dried willow is placed in 500mL of sodium chlorite (2 mol/L) acid solution (0.5 mol/L) for standing for 8h, the acid solution is hydrochloric acid solution, and the treated material is obtained by drying at 100 ℃.
And (3) placing the treatment material in a tubular furnace in an air atmosphere, heating to 250 ℃ at 5 ℃/min, preserving heat for 6 hours, changing into an N 2 atmosphere, and heating to 1500 ℃ at 5 ℃/min, and preserving heat for 3 hours. Cooling to room temperature to obtain the hard carbon anode material.
Example 20
The preparation method of the hard carbon anode material comprises the following steps:
1000g of dried willow is placed in 500mL of sodium chlorite (2 mol/L) acid solution (0.5 mol/L) for standing for 8h, the acid solution is hydrochloric acid solution, and the treated material is obtained by drying at 100 ℃.
And (3) placing the treatment material in a tubular furnace in an air atmosphere, heating to 250 ℃ at 5 ℃/min, preserving heat for 6 hours, changing into an N 2 atmosphere, and heating to 1550 ℃ at 2.5 ℃/min, and preserving heat for 3 hours. Cooling to room temperature to obtain the hard carbon anode material.
Example 21
The preparation method of the hard carbon anode material comprises the following steps:
500g of dried willow and 500g of dried cypress are mixed and placed in 500mL of sodium chlorite (2 mol/L) acid solution (0.5 mol/L) for standing for 8h, wherein the acid solution is nitric acid solution, and the treated material is obtained by drying at 100 ℃.
The treatment material is placed in a tubular furnace in air atmosphere, the temperature is raised to 250 ℃ at 5 ℃/min, the temperature is kept for 6 hours, the temperature is changed into N 2 atmosphere, and the temperature is raised to 1520 ℃ at 2.5 ℃/min, and the temperature is kept for 3 hours. Cooling to room temperature to obtain the hard carbon anode material.
Example 22
The preparation method of the hard carbon anode material comprises the following steps:
500g of dried willow, 250g of dried cypress and 250g of dried pine are mixed and placed in 500mL of sodium chlorite (2 mol/L) acid solution (0.5 mol/L) for 8h, the acid solution is nitric acid solution, and the mixture is dried at 100 ℃ to obtain a treated material.
And (3) placing the treatment material in a tubular furnace in an air atmosphere, heating to 250 ℃ at 5 ℃/min, preserving heat for 6 hours, changing into an N 2 atmosphere, and heating to 1550 ℃ at 2.5 ℃/min, and preserving heat for 3 hours. Cooling to room temperature to obtain the hard carbon anode material.
Comparative example 1
1000G of dried willow is placed in a tube furnace with N 2 atmosphere, and the temperature is raised to 1400 ℃ at 2 ℃/min and is kept for 3 hours. Cooling to room temperature to obtain the hard carbon anode material.
Comparative example 2
1000G of dried willow is placed in a tubular furnace in air atmosphere, the temperature is raised to 250 ℃ at 2 ℃/min, the temperature is kept for 4 hours, the atmosphere is changed into N 2 atmosphere, and the temperature is raised to 1400 ℃ at 2.5 ℃/min, and the temperature is kept for 3 hours. Cooling to room temperature to obtain the hard carbon anode material.
Experimental example
The negative electrode materials of each example and comparative example were prepared to obtain batteries, specifically comprising:
The hard carbon materials prepared in the example or the comparative example are respectively used as active substances to be mixed with a binder CMC, SBR and a conductive agent Super P according to the mass ratio of 90:3:3:4, distilled water is added to prepare negative electrode slurry, an automatic film coating dryer is adopted to uniformly coat the negative electrode slurry on an aluminum foil current collector by using a scraper, the coating thickness is 200+/-1 mu m, and a 14mm diameter circular electrode plate is prepared after vacuum drying.
Sodium metal sheet as positive electrode; the electrolyte is 1M NaFP 6 dissolved in the mixed solution of DMC, EC and EMC, and the volume ratio of DMC, EC and EMC is 1:1:1; the separator was celgard 2400 assembled into half cells for electrochemical testing at a current density of 30 mah.g -1 (0.1C), ranging from 0.001 to 2.0V. The electrochemical performance of the corresponding cell of the hard carbon negative electrode material of example 1 is shown in fig. 2.
The specific capacity and initial effect of each cell at a current density of 30mA/g are shown in Table 1.
Table 1 battery performance
As can be seen from Table 1, the invention uses natural timber as carbon source, adopts sodium chlorite acid solution to carry out chemical treatment on timber, then carries out low-temperature oxidation treatment and high-temperature carbonization treatment, and the obtained hard carbon anode material has high capacity and high coulomb efficiency, the capacity is more than 330mAh/g at the current density of 30mA/g, and the coulomb efficiency is more than 91.5%.
The wood of comparative example 1 was not treated with an acid solution of sodium chlorite and was not subjected to oxidation treatment, and the capacity and coulombic efficiency of the battery prepared from the obtained hard carbon material were significantly reduced. The wood of comparative example 2 was not treated with an acid solution of sodium chlorite, and the capacity and coulombic efficiency of the resulting hard carbon material prepared battery were reduced.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.
Claims (10)
1. The preparation method of the hard carbon anode material is characterized by comprising the following steps of:
placing wood in an acid solution of sodium chlorite for soaking treatment to obtain a treated material;
And sequentially carrying out oxidation treatment and carbonization treatment on the treatment material to obtain the hard carbon anode material.
2. The method for producing a hard carbon anode material according to claim 1, characterized by comprising at least one of the following features (1) to (2):
(1) The wood comprises at least one of elm, willow, oak, walnut, birch, camphorwood, nanmu, boxwood, paulownia, pterocarpus santalinus, rosewood, mahogany, chromowood, pine, cypress, yew, ginkgo, teak and red sandalwood;
(2) The length of the wood is 3-5 cm.
3. The method for producing a hard carbon anode material according to claim 1, characterized by comprising at least one of the following features (1) to (6):
(1) In the acid solution of sodium chlorite, the concentration of sodium chlorite is 0.1-6 mol/L;
(2) In the acid solution of sodium chlorite, the acid concentration is 0.1-3 mol/L;
(3) In the acid solution of sodium chlorite, the acid comprises at least one of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, hydrobromic acid and polyphosphoric acid;
(4) The soaking treatment time is 8-15 h;
(5) After the soaking treatment, the method also comprises a drying treatment;
(6) The temperature of the drying treatment after the soaking treatment is 70-110 ℃.
4. The method for producing a hard carbon anode material according to claim 1, characterized by comprising at least one of the following features (1) to (3):
(1) The heat preservation temperature of the oxidation treatment is 200-300 ℃, and the heat preservation time of the oxidation treatment is 1-12 h;
(2) The atmosphere of the oxidation treatment is air atmosphere;
(3) The temperature rising rate of the oxidation treatment is 1-5 ℃/min.
5. The method for producing a hard carbon anode material according to claim 1, characterized by comprising at least one of the following features (1) to (3):
(1) The heat preservation temperature of the carbonization treatment is 1350-1600 ℃, and the heat preservation time of the carbonization treatment is 2-5 h;
(2) The carbonization treatment atmosphere is a protective gas;
(3) The heating rate of the carbonization treatment is 1-20 ℃/min.
6. The method for producing a hard carbon negative electrode material according to claim 5, characterized by comprising at least one of the following features (1) to (2):
(1) The protective gas includes at least one of Ar, he, N 2、H2、NH3, and CO 2;
(2) After the carbonization treatment, the method further comprises the following steps: the mass was cooled to room temperature.
7. The hard carbon negative electrode material produced by the production method of the hard carbon negative electrode material according to any one of claims 1 to 6.
8. The hard carbon negative electrode material of claim 7, wherein the hard carbon negative electrode material has a capacity of greater than 330mAh/g and a coulombic efficiency of greater than 91.5% at a current density of 30 mA/g.
9. A negative electrode sheet, characterized by comprising the hard carbon negative electrode material produced by the production method of the hard carbon negative electrode material according to any one of claims 1 to 6.
10. A battery comprising the negative electrode sheet according to claim 9.
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| Publication Number | Publication Date |
|---|---|
| CN118270764A true CN118270764A (en) | 2024-07-02 |
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