CN115650205A - Pretreatment method for sodium ion battery negative electrode material - Google Patents
Pretreatment method for sodium ion battery negative electrode material Download PDFInfo
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Abstract
The application discloses a pretreatment method of a sodium ion battery cathode material, which is characterized by comprising the following steps: s1: crushing a coal-based material serving as a raw material to obtain a particle mixture; s2: deashing the particle mixture; s3: drying the deashed particle mixture, and controlling the total water content to be not more than 5%; s4: grinding the dried particle mixture into fine powder with the particle size distribution satisfying D 50 = 5-15 μm; s5: carbonizing the fine powder at low temperature under oxygen isolation; s6: and (3) pickling the fine powder carbonized at low temperature for at least one time and then drying. The method improves various performances of the coal-based material converted into the sodium ion battery cathode material, and reduces the content of impurities in the sodium ion battery cathode material.
Description
Technical Field
The application relates to the field of sodium ion battery materials, in particular to a pretreatment method of a sodium ion battery negative electrode material.
Background
A sodium ion battery is a battery that operates on a principle similar to a lithium ion battery. In recent years, the demand in the field of power batteries is increasing, which leads to short supply of materials for lithium ion batteries, and the research on sodium ion batteries is becoming a hot spot. The sodium ion battery mainly comprises five parts, namely a positive electrode material, a negative electrode material, an electrolyte, a current collector and a diaphragm. The anode and cathode materials affect the key performance indexes of the sodium ion battery, such as energy density, power density, cycle life, safety and the like, and are of great importance to the battery performance.
Different from a graphite material cathode adopted by a lithium ion battery, because the graphite interlayer spacing is too small, the sodium ions with larger radius are embedded between the graphite layers, and the energy is larger, and reversible de-embedding can not be carried out in an effective potential window, so that the traditional graphite can not be used as the cathode of the sodium ion battery.
The sodium ion negative electrode material comprises a carbon-based material, a non-metallic simple substance, an organic compound and a metal oxide, wherein the carbon-based negative electrode material is most widely applied in industrialization. The carbon-based negative electrode material has rich raw material sources, and comprises carbon-containing raw materials such as oil series, coal series, asphalt series, biomass and the like. The biomass is a raw material of the cathode material of the mainstream sodium-ion battery at present due to low impurity content and low processing difficulty. But the high-quality biomass raw materials in China are relatively deficient, and the high-quality biomass raw materials are high in price. Therefore, the development of the sodium ion battery cathode material industry in China is slow all the time, and the sodium ion battery cathode material industry depends on import and has few industrial applications.
China has abundant coal reserves, coal is one of carbon-based raw materials, and the coal is rarely used for preparing carbon-based materials at present due to complex components and high impurity content. In fact, the coal in China is rich in reserves and varieties, and can completely replace biomass to be used as a high-quality raw material to be applied to the preparation of the sodium ion negative electrode material through the pretreatment of the raw material. Once the limitation of raw materials is broken through, the resource utilization of coal and carbon is realized, and the development of the sodium ion battery cathode material industry is greatly promoted.
Disclosure of Invention
In order to prepare a sodium ion negative electrode material precursor meeting performance requirements from common coal-based raw materials, the application provides a pretreatment method of a sodium ion battery negative electrode material.
A pretreatment method of a sodium ion battery negative electrode material comprises the following steps:
s1: crushing a coal-based material serving as a raw material to obtain a particle mixture;
s2: deashing the particle mixture;
s3: drying the particle mixture after deashing, and controlling the total water content to be not more than 5%;
s4: grinding the dried particle mixture into fine powder, wherein the particle size distribution of the fine powder meets D50= 5-15 μm;
s5: carbonizing the fine powder at low temperature under the condition of isolating oxygen;
s6: and (3) pickling the fine powder carbonized at low temperature for at least one time and then drying.
By adopting the technical scheme, most of impurities in the coal-based material can be removed by firstly crushing and then deashing the coal-based material, so that coal-based material powder with higher purity and better fineness is obtained. The total water content of the coal-based material after deashing is not more than 5 percent, and the particle size distribution meets the requirement D 50 And the particle size is 5-15 mu m, so that in the subsequent low-temperature oxygen-isolated carbonization process, the requirement that the contact surface area of the fine powder of the coal-based material is large enough, the carbonization process of the coal-based material cannot be influenced by the contained water, the slow overflow of volatile matters in the low-temperature carbonization process is ensured, and holes which are beneficial to the inlet and outlet of sodium ions are gradually formed on the coal-based material. And finally, at least one time of acid washing is carried out, so that residual metal impurities in the coal-based material are removed, the interlayer framework formed primarily in the low-temperature carbonization process is further stabilized, micropores and small holes are further expanded, more space is reserved for adsorption and desorption of sodium ions in the negative electrode material, and the high-quality sodium ion negative electrode material is finally formed.
Further, the step S5 specifically includes the following steps:
a. heating the fine powder to 450-650 ℃ at a heating rate of 5-10 ℃/min under the condition of isolating oxygen;
b. and (3) carrying out heat preservation treatment on the heated fine powder for 0.5-1 h, and controlling the volatile component to be less than 10%.
By adopting the technical scheme, the coal-based material is heated to 450-650 ℃ at the heating rate of 5-10 ℃/min under the condition of isolating oxygen, in the heating process,
further, the fine powder is pretreated before the temperature rise process, and the pretreatment step comprises the following steps:
a. the fine powder and sodium stearate are uniformly mixed according to the mass ratio of 10-20: 1;
b. putting the uniformly mixed materials into a heating tank with constant pressure and high pressure, and compacting the materials;
c. preheating for 0.5h at 260-300 ℃ and then carrying out the subsequent low-temperature carbonization step;
and in the temperature rise process, maintaining the pressure of the material unchanged.
By adopting the technical scheme, the disorder degree of fine powder prepared from the coal-based material is improved by pressurizing and adding the sodium stearate, the ordered arrangement of carbon is not easy to occur, and the sodium storage performance of the carbonized coal-based material is improved. And secondly, the specific surface area of the coal-based material fine powder in the carbonization process can be obviously reduced in a pressurization mode, the specific surface area is favorable for reducing the contact area between the coal-based material and an electrolyte after the coal-based material forms a sodium ion negative electrode material, the SEI (solid electrolyte interphase) formation is reduced, and the first cycle coulomb efficiency of the negative electrode material is improved.
And further, the volatile matters overflowing in the step S5 are purified and then returned to the step S5 for heat supply.
By adopting the technical scheme, the overflowed volatile matter can supply heat for the step S5, so that the recycling efficiency of resources is improved, and the green development is met.
Further, the acid adopted in the acid cleaning in the S6 is one or more selected from hydrofluoric acid, hydrochloric acid, nitric acid and sulfuric acid.
Furthermore, in the S6, the acid washing is carried out in a gradient acid washing mode.
By adopting the technical scheme, the secondary pickling solution can be used as primary pickling in a step pickling manner, so that the acid consumption is greatly reduced, the utilization efficiency of resources is greatly improved on the premise of not influencing the pickling effect, and the zero discharge of waste water is basically realized.
Further, the coal-based material is selected from one or more of subbituminous coal, lignite, bituminous coal and anthracite.
Further, the particle size of the crushed particle mixture of the coal-based material in S1 is not more than 10mm.
Furthermore, the tail gas in the S5 medium-low temperature carbonization system can supply heat to the drying system through heat exchange.
By adopting the technical scheme, the waste heat can obtain higher utilization efficiency, the energy gradient utilization is realized, the energy is further saved, the concentration of magnetic substances in the prepared sodium ion negative electrode material is controlled to be not more than 30ppm, the concentrations of limited substances such as cadmium, lead and mercury and compounds are controlled to be not more than 3ppm, and the concentrations of negative ion substances such as fluorine, chlorine, bromine, iodine and sulfate radicals are controlled to be not more than 10ppm.
By adopting the technical scheme, the prepared sodium ion negative electrode material has extremely low impurity content and can be better applied to a sodium ion battery.
In summary, the present application has the following beneficial effects:
according to the method, the coal-based material is effectively converted into the sodium-ion battery cathode material meeting the specification through the steps of deashing, grinding and the like of the coal-based material and then low-temperature carbonization and the like. And various performances of the coal-based material after being converted into the negative electrode material of the sodium-ion battery are improved and the content of impurities in the negative electrode material is reduced through a pretreatment step before low-temperature carbonization and a pressurization sealing mode.
Detailed Description
The present application will be described in further detail with reference to examples.
Example 1
A pretreatment method of a sodium-ion battery negative electrode material comprises the following steps:
s1: taking a coal-based material as a raw material, and circularly crushing the coal-based material by a crushing system to obtain a particle mixture with the particle size of 10 mm; anthracite is selected as the coal-based material.
S2: performing deliming treatment on the particle mixture through a deliming system according to different ash density properties, and separating to obtain a delimed particle mixture;
s3: drying the deashed particle mixture to obtain a dried particle mixture, and controlling the total water content to be not more than 5%;
s4: grinding the dried particle mixture into fine powder by a grinding system, wherein the particle size distribution of the fine powder satisfies D 50 ＝10μm；
S5: carbonizing the fine powder at low temperature under the condition of isolating oxygen; the initial temperature of the fine powder is 40 ℃, the heating rate is controlled to be 10 ℃/min, the temperature is raised to 640 ℃, the heating time is 1h, and the heat is preserved for 0.5h; the discharged volatile matter is 8%.
S6: and (3) carrying out gradient acid washing on the fine powder after low-temperature carbonization for three times, and then drying.
Example 2
A pretreatment method of a sodium ion battery negative electrode material comprises the following steps:
s1: taking a coal-based material as a raw material, and circularly crushing the coal-based material by a crushing system to obtain a particle mixture with the particle size of 10 mm; the coal-based material is subbituminous coal.
S2: performing deliming treatment on the particle mixture through a deliming system according to different properties of ash density, and separating to obtain a delimed particle mixture;
s3: drying the deashed particle mixture to obtain a dried particle mixture, and controlling the total water content to be not more than 5%;
s4: grinding the dried particle mixture into fine powder by a grinding system, wherein the particle size distribution of the fine powder satisfies D 50 ＝10μm；
S5: carbonizing the fine powder at low temperature under oxygen isolation; the initial temperature of the fine powder is 40 ℃, the heating rate is controlled to be 10 ℃/min, the temperature is raised to 640 ℃, the heating time is 1h, and the heat is preserved for 0.5h; the discharge volatile matter was 9%.
S6: and (3) carrying out gradient acid washing on the fine powder after low-temperature carbonization for three times, and then drying.
Example 3
A pretreatment method of a sodium ion battery negative electrode material comprises the following steps:
s1: taking a coal-based material as a raw material, and circularly crushing the coal-based material by a crushing system to obtain a particle mixture with the particle size of 10 mm; the coal-based material is lignite.
S2: performing deliming treatment on the particle mixture through a deliming system according to different ash density properties, and separating to obtain a delimed particle mixture;
s3: drying the deashed particle mixture to obtain a dried particle mixture, and controlling the total water content to be not more than 5%;
s4: grinding the dried particle mixture into fine powder by a grinding system, wherein the particle size distribution of the fine powder satisfies D 50 ＝10μm；
S5: carbonizing the fine powder at low temperature under the condition of isolating oxygen; the initial temperature of the fine powder is 40 ℃, the heating rate is controlled to be 10 ℃/min, the temperature is raised to 640 ℃, the heating time is 1h, and the temperature is kept for 0.5h; the discharged volatile matter is 10%.
S6: and (3) carrying out gradient acid washing on the fine powder after low-temperature carbonization for three times, and then drying.
Example 4
A pretreatment method of a sodium-ion battery negative electrode material comprises the following steps:
s1: taking a coal-based material as a raw material, and circularly crushing the coal-based material by a crushing system to obtain a particle mixture with the particle size of 10 mm; the coal-based material is selected from bituminous coal.
S2: performing deliming treatment on the particle mixture through a deliming system according to different properties of ash density, and separating to obtain a delimed particle mixture;
s3: drying the deashed particle mixture to obtain a dried particle mixture, and controlling the total water content to be not more than 5%;
s4: grinding the dried particle mixture into fine powder by a grinding system, wherein the particle size distribution of the fine powder satisfies D 50 ＝10μm；
S5: carbonizing the fine powder at low temperature under oxygen isolation; the initial temperature of the fine powder is 40 ℃, the heating rate is controlled to be 10 ℃/min, the temperature is raised to 640 ℃, the heating time is 1h, and the heat is preserved for 0.5h; the discharged volatile matter is 10%.
S6: and (3) carrying out gradient acid washing on the fine powder after low-temperature carbonization for three times, and then drying.
Example 5
A pretreatment method of a sodium-ion battery negative electrode material comprises the following steps:
s1: taking a coal-based material as a raw material, and circularly crushing the coal-based material by a crushing system to obtain a particle mixture with the particle size of 10 mm; anthracite is selected as the coal-based material.
S2: performing deliming treatment on the particle mixture through a deliming system according to different properties of ash density, and separating to obtain a delimed particle mixture;
s3: drying the deashed particle mixture to obtain a dried particle mixture, and controlling the total water content to be not more than 5%;
s4: grinding the dried particle mixture into fine powder by a grinding system, wherein the particle size distribution of the fine powder satisfies D 50 ＝5μm；
S5: carbonizing the fine powder at low temperature under oxygen isolation; the initial temperature of the fine powder is 50 ℃, the heating rate is controlled to be 10 ℃/min, the temperature is increased to 650 ℃, the heating time is 1h, and the temperature is kept for 0.5h; the discharged volatile matter is 10%.
S6: and (3) carrying out gradient acid washing on the fine powder after low-temperature carbonization for three times, and then drying.
Example 6
A pretreatment method of a sodium ion battery negative electrode material comprises the following steps:
s1: taking a coal-based material as a raw material, and circularly crushing the coal-based material by a crushing system to obtain a particle mixture with the particle size of 10 mm; anthracite is selected as the coal-based material.
S2: performing deliming treatment on the particle mixture through a deliming system according to different properties of ash density, and separating to obtain a delimed particle mixture;
s3: drying the deashed particle mixture to obtain a dried particle mixture, and controlling the total water content to be not more than 5%;
s4: grinding the dried particle mixture into fine powder by a grinding system, wherein the particle size distribution of the fine powder satisfies D 50 ＝7μm；
S5: carbonizing the fine powder at low temperature under the condition of isolating oxygen; the initial temperature of the fine powder is 40 ℃, the heating rate is controlled to be 10 ℃/min, the temperature is raised to 520 ℃, the heating time is 0.8h, and the temperature is kept for 0.8h; the discharge volatile matter was 7%.
S6: and (3) carrying out gradient acid washing on the fine powder after low-temperature carbonization for three times, and then drying.
Example 7
A pretreatment method of a sodium-ion battery negative electrode material comprises the following steps:
s1: taking a coal-based material as a raw material, and circularly crushing the coal-based material by a crushing system to obtain a particle mixture with the particle size of 10 mm; the coal-based material is anthracite.
S2: performing deliming treatment on the particle mixture through a deliming system according to different ash density properties, and separating to obtain a delimed particle mixture;
s3: drying the deashed particle mixture to obtain a dried particle mixture, and controlling the total water content to be not more than 5%;
s4: grinding the dried particle mixture into fine powder by a grinding system, wherein the particle size distribution of the fine powder satisfies D 50 ＝13μm；
S5: carbonizing the fine powder at low temperature under the condition of isolating oxygen; the initial temperature of the fine powder is 40 ℃, the heating rate is controlled to be 10 ℃/min, the temperature is raised to 460 ℃, the heating time is 0.7h, and the temperature is kept for 1h; the discharged volatile matter is 5%.
S6: and (3) carrying out gradient acid washing on the fine powder after low-temperature carbonization for three times, and then drying.
Example 8
A pretreatment method of a sodium-ion battery negative electrode material comprises the following steps:
s1: taking a coal-based material as a raw material, and circularly crushing the coal-based material by a crushing system to obtain a particle mixture with the particle size of 10 mm; anthracite is selected as the coal-based material.
S2: performing deliming treatment on the particle mixture through a deliming system according to different properties of ash density, and separating to obtain a delimed particle mixture;
s3: drying the deashed particle mixture to obtain a dried particle mixture, and controlling the total water content to be not more than 5%;
s4: grinding the dried particle mixture into fine powder by a grinding system, wherein the particle size distribution of the fine powder satisfies D 50 ＝15μm；
S5: carbonizing the fine powder at low temperature under the condition of isolating oxygen; the initial temperature of the fine powder is 140 ℃, the heating rate is controlled to be 10 ℃/min, the temperature is increased to 500 ℃, the heating time is 0.6h, and the temperature is kept for 0.9h; the discharged volatile matter is 6%.
S6: and (3) carrying out gradient acid washing on the fine powder after low-temperature carbonization for three times, and then drying.
Example 9
A pretreatment method of a sodium-ion battery negative electrode material comprises the following steps:
s1: taking a coal-based material as a raw material, and circularly crushing the coal-based material by a crushing system to obtain a particle mixture with the particle size of 10 mm; anthracite is selected as the coal-based material.
S2: performing deliming treatment on the particle mixture through a deliming system according to different properties of ash density, and separating to obtain a delimed particle mixture;
s3: drying the deashed particle mixture to obtain a dried particle mixture, and controlling the total water content to be not more than 5%;
s4: grinding the dried particle mixture into fine powder by a grinding system, wherein the particle size distribution of the fine powder satisfies D 50 ＝10μm；
S5: carbonizing the fine powder at low temperature under oxygen isolation; the initial temperature of the fine powder is 180 ℃, the heating rate is controlled to be 10 ℃/min, the temperature is increased to 480 ℃, the heating time is 0.5h, and the temperature is kept for 0.8h; the discharge volatile matter is 6%.
S6: and (3) carrying out gradient acid washing on the fine powder after low-temperature carbonization for three times, and then drying.
Example 10
A pretreatment method of a sodium ion battery negative electrode material comprises the following steps:
s1: taking a coal-based material as a raw material, and circularly crushing the coal-based material by a crushing system to obtain a particle mixture with the particle size of 10 mm; anthracite is selected as the coal-based material.
S2: performing deliming treatment on the particle mixture through a deliming system according to different ash density properties, and separating to obtain a delimed particle mixture;
s3: drying the deashed particle mixture to obtain a dried particle mixture, and controlling the total water content to be not more than 5%;
s4: grinding the dried particle mixture into fine powder by a grinding system, wherein the particle size distribution of the fine powder satisfies D 50 ＝10μm；
S5: carbonizing the fine powder at low temperature under oxygen isolation; the initial temperature of the fine powder is 150 ℃, the heating rate is controlled to be 5 ℃/min, the temperature is increased to 450 ℃, the heating time is 1h, and the temperature is kept for 1h; the volatile matter of the discharged material is 5 percent.
S6: and (3) carrying out gradient acid washing on the fine powder after low-temperature carbonization for three times, and then drying.
Example 11
A pretreatment method of a sodium-ion battery negative electrode material comprises the following steps:
s1: taking a coal-based material as a raw material, and circularly crushing the coal-based material by a crushing system to obtain a particle mixture with the particle size of 10 mm; the coal-based material is anthracite.
S2: performing deliming treatment on the particle mixture through a deliming system according to different properties of ash density, and separating to obtain a delimed particle mixture;
s3: drying the deashed particle mixture to obtain a dried particle mixture, and controlling the total water content to be not more than 5%;
s4: grinding the dried particle mixture into fine powder by a grinding system, wherein the particle size distribution of the fine powder satisfies D 50 ＝10μm；
S5: carbonizing the fine powder at low temperature under oxygen isolation; the initial temperature of the fine powder is 120 ℃, the heating rate is controlled to be 6 ℃/min, the temperature is increased to 480 ℃, the heating time is 1h, and the temperature is kept for 0.8h; the discharged volatile matter is 5%.
S6: and (3) carrying out gradient acid washing on the fine powder after low-temperature carbonization for three times, and then drying.
Example 12
A pretreatment method of a sodium ion battery negative electrode material comprises the following steps:
s1: taking a coal-based material as a raw material, and circularly crushing the coal-based material by a crushing system to obtain a particle mixture with the particle size of 10 mm; the coal-based material is anthracite.
S2: performing deliming treatment on the particle mixture through a deliming system according to different properties of ash density, and separating to obtain a delimed particle mixture;
s3: drying the deashed particle mixture to obtain a dried particle mixture, and controlling the total water content to be not more than 5%;
s4: grinding the dried particle mixture into fine powder with full particle size distribution by a grinding systemFoot D 50 ＝10μm；
S5: carbonizing the fine powder at low temperature under oxygen isolation; the initial temperature of the fine powder is 100 ℃, the heating rate is controlled to be 7 ℃/min, the temperature is raised to 520 ℃, the heating time is 1h, and the temperature is kept for 0.6h; the discharge volatile matter was 7%.
S6: and (3) carrying out gradient acid washing on the fine powder after low-temperature carbonization for three times, and then drying.
Example 13
A pretreatment method of a sodium-ion battery negative electrode material comprises the following steps:
s1: taking a coal-based material as a raw material, and circularly crushing the coal-based material by a crushing system to obtain a particle mixture with the particle size of 10 mm; anthracite is selected as the coal-based material.
S2: performing deliming treatment on the particle mixture through a deliming system according to different properties of ash density, and separating to obtain a delimed particle mixture;
s3: drying the deashed particle mixture to obtain a dried particle mixture, and controlling the total water content to be not more than 5%;
s4: grinding the dried particle mixture into fine powder by a grinding system, wherein the particle size distribution of the fine powder satisfies D 50 ＝10μm；
S5: carbonizing the fine powder at low temperature under the condition of isolating oxygen; the initial temperature of the fine powder is 80 ℃, the heating rate is controlled to be 8 ℃/min, the temperature is raised to 560 ℃, the heating time is 1h, and the temperature is kept for 0.8h; the volatile matter discharged is 8 percent.
S6: and (3) carrying out gradient acid washing on the fine powder after low-temperature carbonization for three times, and then drying.
Example 14
A pretreatment method of a sodium ion battery negative electrode material comprises the following steps:
s1: taking a coal-based material as a raw material, and circularly crushing the coal-based material by a crushing system to obtain a particle mixture with the particle size of 10 mm; anthracite is selected as the coal-based material.
S2: performing deliming treatment on the particle mixture through a deliming system according to different properties of ash density, and separating to obtain a delimed particle mixture;
s3: drying the deashed particle mixture to obtain a dried particle mixture, and controlling the total water content to be not more than 5%;
s4: grinding the dried particle mixture into fine powder by a grinding system, wherein the particle size distribution of the fine powder satisfies D 50 ＝10μm；
S5: carbonizing the fine powder at low temperature under oxygen isolation; the initial temperature of the fine powder is 60 ℃, the heating rate is controlled to be 9 ℃/min, the temperature is raised to 600 ℃, the heating time is 1h, and the temperature is kept for 0.8h; the discharged volatile matter was 9%.
S6: and (3) carrying out gradient acid washing on the fine powder after low-temperature carbonization for three times, and then drying.
Example 15
A pretreatment method of a sodium ion battery negative electrode material comprises the following steps:
s1: taking a coal-based material as a raw material, and circularly crushing the coal-based material by a crushing system to obtain a particle mixture with the particle size of 10 mm; anthracite is selected as the coal-based material.
S2: performing deliming treatment on the particle mixture through a deliming system according to different ash density properties, and separating to obtain a delimed particle mixture;
s3: drying the deashed particle mixture to obtain a dried particle mixture, and controlling the total water content to be not more than 5%;
s4: grinding the dried particle mixture into fine powder by a grinding system, wherein the particle size distribution of the fine powder satisfies D 50 ＝10μm；
S5: carbonizing the fine powder at low temperature under oxygen isolation; the initial temperature of the fine powder is 210 ℃, the heating rate is controlled to be 7 ℃/min, the temperature is raised to 630 ℃, the heating time is 1h, and the temperature is kept for 0.8h; the discharged volatile matter was 9%.
S6: and (3) carrying out gradient acid washing on the fine powder after low-temperature carbonization for three times, and then drying.
Example 16
Example 16 differs from example 1 in that the fine powder is subjected to a pretreatment before the temperature is raised in step S5, the pretreatment step comprising the steps of:
step a, uniformly mixing the fine powder and sodium stearate according to the mass ratio of 10: 1;
b, filling the uniformly mixed materials into a heating tank with the constant pressure of 1.3MPa, and compacting the materials;
and c, preheating for 1h at 260 ℃ and then carrying out a subsequent low-temperature carbonization step.
Example 17
Example 17 differs from example 1 in that the fine powder is pretreated before the temperature is raised in step S5, and the pretreatment step includes the steps of:
step a, uniformly mixing the fine powder and sodium stearate according to the mass ratio of 13: 1;
b, filling the uniformly mixed materials into a heating tank with the constant pressure of 1.3MPa, and compacting the materials;
and c, preheating for 1h at 260 ℃ and then carrying out a subsequent low-temperature carbonization step.
Example 18
Example 18 differs from example 1 in that the fine powder is pretreated before the temperature is raised in step S5, and the pretreatment step includes the steps of:
step a, uniformly mixing the fine powder and sodium stearate according to the mass ratio of 15: 1;
b, filling the uniformly mixed materials into a heating tank with the constant pressure of 1.3MPa, and compacting the materials;
and c, preheating for 1h at 260 ℃ and then carrying out subsequent low-temperature carbonization.
Example 19
Example 19 differs from example 1 in that the fine powder is subjected to a pretreatment before the temperature is raised in step S5, the pretreatment step comprising the steps of:
step a, uniformly mixing the fine powder and sodium stearate according to the mass ratio of 18: 1;
b, filling the uniformly mixed materials into a heating tank with the constant pressure of 1.3MPa, and compacting the materials;
and c, preheating for 1h at 260 ℃ and then carrying out subsequent low-temperature carbonization.
Example 20
Example 20 differs from example 1 in that the fine powder is subjected to a pretreatment before the temperature is raised in step S5, the pretreatment comprising the steps of:
step a, uniformly mixing the fine powder and sodium stearate according to the mass ratio of 20: 1;
b, filling the uniformly mixed materials into a heating tank with the constant pressure of 1.4MPa, and compacting the materials;
and c, preheating for 1h at 260 ℃ and then carrying out subsequent low-temperature carbonization.
Example 21
Example 21 differs from example 1 in that the fine powder is subjected to a pretreatment before the temperature is raised in step S5, the pretreatment step comprising the steps of:
step a, uniformly mixing the fine powder and sodium stearate according to the mass ratio of 20: 1;
b, filling the uniformly mixed materials into a heating tank with the constant pressure of 1.5MPa, and compacting the materials;
and c, preheating for 1h at 260 ℃ and then carrying out a subsequent low-temperature carbonization step.
Example 22
Example 22 differs from example 1 in that the fine powder is pretreated before the temperature is raised in step S5, and the pretreatment step includes the steps of:
step a, uniformly mixing the fine powder and sodium stearate according to the mass ratio of 20: 1;
b, filling the uniformly mixed materials into a heating tank with the constant pressure of 1.2MPa, and compacting the materials;
and c, preheating for 1h at 260 ℃ and then carrying out subsequent low-temperature carbonization.
Example 23
Example 23 differs from example 1 in that the fine powder is subjected to a pretreatment before the temperature is raised in step S5, the pretreatment step comprising the steps of:
step a, uniformly mixing the fine powder and sodium stearate according to the mass ratio of 20: 1;
b, filling the uniformly mixed materials into a heating tank with the constant pressure of 0.8MPa, and compacting the materials;
and c, preheating for 1h at 260 ℃ and then carrying out a subsequent low-temperature carbonization step.
Example 24
Example 24 differs from example 1 in that the fine powder is subjected to a pretreatment before the temperature is raised in step S5, the pretreatment comprising the steps of:
step a, uniformly mixing the fine powder and sodium stearate according to the mass ratio of 20: 1;
b, filling the uniformly mixed materials into a heating tank with the constant pressure of 1.5MPa, and compacting the materials;
and c, preheating for 0.8h at 270 ℃ and then carrying out a subsequent low-temperature carbonization step.
Example 25
Example 25 differs from example 1 in that the fine powder is subjected to a pretreatment before the temperature is raised in step S5, the pretreatment step comprising the steps of:
step a, uniformly mixing the fine powder and sodium stearate according to the mass ratio of 20: 1;
b, filling the uniformly mixed materials into a heating tank with the constant pressure of 1.5MPa, and compacting the materials;
and c, preheating for 0.7h at 280 ℃ and then carrying out a subsequent low-temperature carbonization step.
Example 26
Example 26 differs from example 1 in that the fine powder is pretreated before the temperature is raised in step S5, and the pretreatment step includes the steps of:
step a, uniformly mixing the fine powder and sodium stearate according to the mass ratio of 20: 1;
b, filling the uniformly mixed materials into a heating tank with the constant pressure of 1.5MPa, and compacting the materials;
and c, preheating for 0.5h at 300 ℃, and then carrying out a subsequent low-temperature carbonization step.
Comparative example
Comparative example 1
The difference from example 1 is that the deliming treatment of step S2 was not performed.
Comparative example 2
The difference from example 1 is that the fine powder D after grinding in step S4 50 ＝3μm。
Comparative example 3
The difference from example 1 is that the fine powder D after grinding in step S4 50 ＝20μm。
Comparative example 4
The difference from example 1 is that no acid washing is carried out in step S6, but a rinsing with deionized water is carried out.
Performance test
Comparing the main flow indexes of the coal-based sodium ion battery negative electrode material prepared in the embodiment 1 with those of a commercial carbon-based sodium ion battery negative electrode material:
and (4) conclusion: as can be seen from the above table, each index of the coal-based sodium ion battery negative electrode material prepared in the embodiment of the application is more excellent than that of the conventional coal-based sodium ion battery negative electrode material. And the content of various impurities is also in a lower level, so that the composite material is very suitable for being used as a coal-based sodium ion battery cathode material to replace the traditional coal-based sodium ion battery cathode material.
And (4) conclusion: as can be seen from comparison of the above examples 1-25 with the comparative example 1, the deliming treatment and the grinding fineness in the present application have a large influence on the performance of the finally prepared negative electrode material, and need to be controlled within a proper range. While examples 1-25 are compared with comparative examples 2-3, it can be seen that the fine powder D after grinding 50 The size also has a great influence on the performance of the finally prepared cathode material. In contrast, when examples 1 to 25 are compared with comparative example 4, it can be seen that the acid washing step has a large influence on the properties of the finally obtained anode material. Secondly, as can be seen from the comparison between examples 14 to 25 and example 1, the pretreatment step in the application can significantly reduce the specific surface area of the coal-based material after being prepared into the sodium-ion negative electrode material, thereby improving the first performance of the sodium-ion batteryCoulomb efficiency, reduced capacity loss.
The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.
Claims (10)
1. The pretreatment method of the negative electrode material of the sodium-ion battery is characterized by comprising the following steps of:
s1: crushing a coal-based material serving as a raw material to obtain a particle mixture;
s2: deashing the particle mixture;
s3: drying the deashed particle mixture, and controlling the total water content to be not more than 5%;
s4: grinding the dried particle mixture into fine powder, wherein the particle size distribution of the fine powder meets D50= 5-15 μm;
s5: carbonizing the fine powder at low temperature under the condition of isolating oxygen;
s6: and (3) carrying out acid washing on the fine powder after low-temperature carbonization for at least one time, and then drying.
2. The pretreatment method of the anode material of the sodium-ion battery according to claim 1, wherein the step S5 specifically comprises the following steps:
step a, heating the fine powder to 450-650 ℃ at a heating rate of 5-10 ℃/min under the condition of isolating oxygen;
and b, preserving the heat of the heated fine powder for 0.5 to 1 hour, and controlling the volatile matter to be less than 10 percent.
3. The pretreatment method of the anode material of the sodium-ion battery as claimed in claim 2, wherein the fine powder is pretreated before the temperature rising process, and the pretreatment step comprises the following steps:
a. the fine powder and sodium stearate are uniformly mixed according to the mass ratio of 10-20: 1;
b. loading the uniformly mixed materials into a constant-pressure and high-pressure heating tank, and compacting the materials;
c. preheating for 0.5h at 260-300 ℃ and then carrying out the subsequent low-temperature carbonization step;
and in the temperature rise process, maintaining the pressure of the material unchanged.
4. The method for pretreating the negative electrode material of the sodium-ion battery according to claim 2, wherein the volatile matters overflowing from the step S5 are purified and then returned to the step S5 for heat supply.
5. The pretreatment method of the sodium-ion battery negative electrode material according to claim 1, wherein the acid adopted in the acid washing in the S6 is one or more selected from hydrofluoric acid, hydrochloric acid, nitric acid and sulfuric acid.
6. The pretreatment method for the anode material of the sodium-ion battery according to claim 1, wherein the acid washing in the step S6 is performed in a gradient acid washing manner.
7. The pretreatment method of a negative electrode material of a sodium-ion battery according to claim 1, wherein the coal-based material is selected from one or more of sub-bituminous coal, lignite, bituminous coal and anthracite coal.
8. The pretreatment method of the anode material for the sodium-ion battery according to claim 1, wherein the particle size of the crushed particle mixture of the coal-based material in S1 is not more than 10mm.
9. The pretreatment method for the cathode material of the sodium-ion battery according to claim 1, wherein the tail gas in the low-temperature carbonization system in S5 can supply heat to a drying system through heat exchange.
10. The pretreatment method of the sodium-ion battery negative electrode material according to claim 1, characterized in that the concentration of the prepared sodium-ion negative electrode material is controlled to be not more than 30ppm, the concentrations of limited substances such as cadmium, lead and mercury and compounds are controlled to be not more than 3ppm, and the concentrations of negative ion substances such as fluorine, chlorine, bromine, iodine and sulfate radicals are controlled to be not more than 10ppm.
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| CN114044513A (en) * | 2021-11-11 | 2022-02-15 | 博尔特新材料(银川)有限公司 | Preparation method of coal-based graphite/carbon composite negative electrode material for power type lithium ion battery |
| CN114335522A (en) * | 2021-12-31 | 2022-04-12 | 上海杉杉新材料有限公司 | Coal-based carbon negative electrode material, preparation method and application thereof, and battery containing coal-based carbon negative electrode material |
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| WO2015089900A1 (en) * | 2013-12-16 | 2015-06-25 | Xiaohui Chen | Coal carbonization retorts and systems, and coal carbonization process |
| CN108455555A (en) * | 2018-01-18 | 2018-08-28 | 新疆大学 | High-volume and capacity ratio coal based super capacitor electrode material and preparation method thereof |
| CN111293309A (en) * | 2020-03-04 | 2020-06-16 | 溧阳中科海钠科技有限责任公司 | Performance improvement method and application of coal-based sodium ion battery negative electrode material |
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