CN114335484A - Negative electrode composite material for alkali metal ion battery, preparation method of negative electrode composite material and alkali metal ion battery - Google Patents
Negative electrode composite material for alkali metal ion battery, preparation method of negative electrode composite material and alkali metal ion battery Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 62
- 229910001413 alkali metal ion Inorganic materials 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 34
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 31
- 239000007773 negative electrode material Substances 0.000 claims abstract description 30
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 24
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- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 4
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Images
Abstract
The invention belongs to the technical field of alkali metal ion batteries, and particularly relates to a negative electrode composite material for an alkali metal ion battery, a preparation method of the negative electrode composite material, and the alkali metal ion battery. The preparation method of the negative electrode composite material for the alkali metal ion battery comprises the following steps: 1) mixing a bismuth source, graphite, phenolic resin powder and a liquid dispersant to prepare paste, and stirring and scattering the paste to obtain a powdery mixture; the bismuth source is bismuth or bismuth oxide or bismuth chloride; 2) hot pressing the obtained powdery mixture into a rod-shaped composite rod; 3) sintering the prepared composite rod at 600-850 ℃ for 4-8h to obtain an anode rod; 4) and (3) taking the anode rod as an anode and the graphite rod as a cathode, carrying out arc discharge in an arc discharge device at a current of 15-22A, and collecting the deposit to obtain the graphite electrode. The composite negative electrode material has high specific capacity and can effectively relieve the volume expansion effect in the charging and discharging processes.
Description
Technical Field
The invention belongs to the technical field of alkali metal ion batteries, and particularly relates to a negative electrode composite material for an alkali metal ion battery, a preparation method of the negative electrode composite material, and the alkali metal ion battery.
Background
Lithium ion batteries are widely applied in many fields, but have the problems of lithium resource shortage, high cost, poor safety performance and the like, and the development of a secondary battery system with excellent comprehensive performance of the next generation is urgently needed. The sodium/potassium ion battery has the advantages of abundant sodium and potassium resources, low cost, environmental friendliness and similar physical and chemical properties with lithium, and has a huge application space in the fields of large-scale energy storage systems and power supplies of electric automobiles.
The working principle of the sodium/potassium ion battery is similar to that of the lithium ion battery, and the charge and discharge are realized by utilizing the process of deintercalation of sodium/potassium ions between the anode and the cathode. However, sodium/potassium ions have a larger ionic radius and a slower kinetic rate than lithium ion radius, and become major factors that restrict the development of sodium/potassium storage materials. Accordingly, the graphite material has poor cycling stability and small specific capacity when used as a sodium/potassium ion negative electrode due to the small interlayer spacing and the low theoretical capacity (372 mAh/g), and cannot meet the continuously increasing industrialization demand.
The bismuth-based negative electrode material belongs to an alloy type or conversion type negative electrode material, has ultrahigh theoretical specific capacity and good electrochemical behavior, and becomes a research hotspot of a chargeable alkali metal negative electrode material. However, bismuth metal is easy to generate a large volume expansion effect in the alloying/dealloying process, so that electrode materials are pulverized to be stripped and fallen off from a current collector, thereby causing rapid attenuation of battery capacity and poor cycling stability.
In order to improve the volume expansion problem of bismuth-based negative electrode materials in the electrochemical charge-discharge de-intercalation process, a common method is to control the size of the materials to be in a nanometer scale. However, the nano-sized metal negative electrode is very easily agglomerated into larger-sized particles during the cycle, thereby destroying the nano-structure of the material, resulting in deterioration of the cycle performance of the negative electrode material.
Disclosure of Invention
The invention aims to provide a negative electrode composite material for an alkali metal ion battery, a preparation method of the negative electrode composite material and the alkali metal ion battery.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
a preparation method of a negative electrode composite material for an alkali metal ion battery comprises the following steps:
1) mixing a bismuth source, graphite, phenolic resin powder and a liquid dispersant to prepare paste, and stirring and scattering the paste to obtain a powdery mixture; the bismuth source is bismuth or bismuth oxide or bismuth chloride;
2) hot-pressing the powdery mixture prepared in the step 1) into a rod-shaped composite rod;
3) sintering the composite rod prepared in the step 2) at the temperature of 600-850 ℃ for 4-8h to obtain an anode rod;
4) taking the anode rod in the step 3) as an anode, taking a graphite rod as a cathode, carrying out arc discharge in an arc discharge device at a current of 15-22A, and collecting the deposit to obtain the graphite electrode.
The carbon-coated bismuth-based composite negative electrode material is prepared by combining the carbon coating and the arc method, and when the negative electrode material is applied to the negative electrode material of a sodium/potassium ion battery, the negative electrode material has high specific capacity and can effectively relieve the volume expansion effect in the charging and discharging processes, so that the negative electrode material has excellent electrochemical performance. And the preparation process is simple and economic, green and environment-friendly, and is suitable for batch production.
The alkali metal ion battery is a sodium ion battery or a potassium ion battery.
In the step 1), the mass ratio of the bismuth source to the graphite to the phenolic resin powder is 4-10:2-5: 2-3.
The mass ratio of the liquid dispersant to the bismuth source in the step 1) is 1-5: 4-10. The liquid dispersant is at least one of ethyl acetate and dibutyl ester. Preferably, the liquid dispersant consists of ethyl acetate and dibutyl ester in a mass ratio of 2: 1.
In the step 1), a complexing agent is added when a bismuth source, graphite, phenolic resin powder and a liquid dispersing agent are mixed, wherein the complexing agent is at least one of selenium powder, sulfur powder, tellurium powder and phosphorus powder; the mass ratio of the complexing agent to the bismuth source is 4-8: 4-10. Preferably, the complexing agent consists of selenium powder, sulfur powder and tellurium powder in a mass ratio of 2:1: 1.
In the step 1), titanium dioxide is added when the bismuth source, graphite, phenolic resin powder and liquid dispersant are mixed, and the mass ratio of the titanium dioxide to the bismuth source is 2-3: 4-10.
The rotating speed when the paste is stirred and broken up in the step 1) is 5000-.
The pressure in the hot pressing in the step 2) is 0.1-10MPa, preferably 1-2 MPa. The hot-pressing temperature is 50-270 ℃, the preferred temperature is 160-180 ℃, and the more preferred temperature is 170-175 ℃. The hot pressing time is 1-1.5 h. A die with a cylindrical cavity is adopted during hot pressing, and the inner diameter of the cylindrical cavity is 5 mm.
The temperature rise rate of the tubular furnace in the step 3) when the temperature rises to 600-850 ℃ is 1-2 ℃/min, preferably 2 ℃/min. The temperature rise rate in the carbonization process cannot be too fast, otherwise cracks can appear on the surface of the anode rod.
Further, the sintering temperature is 750-800 ℃. Further, the sintering temperature was 800 ℃. The sintering time is 4-8h, preferably 6-7 h. And cooling to room temperature along with the furnace after sintering.
The distance between the anode and the cathode in the step 4) is 1-2 mm. Further, the distance between the two is 2 mm. Preferably, the cathode rod and the anode rod are coaxially arranged.
The time of arc discharge in the step 4) is 30-45 min. Preferably 30-35 min. The current is preferably 20-22A.
And 4) filling argon in a sealed cavity of the arc discharge device provided with the cathode bar and the anode bar during arc discharge. The pressure of argon was 0.01 MPa. Furthermore, the sealed cavity is firstly vacuumized to-0.09 to-0.1 MPa (the pressure is infinitely close to 0.1 MPa), and then argon is filled to exhaust air. This evacuation and argon filling operation was repeated three times. When the argon gas is filled to exhaust the air, the argon gas is filled until the pressure is 0.1 MPa. And after the arc discharge is finished, naturally cooling to room temperature, and then closing the cooling water. When the deposition product is collected, the product on both the bottom wall and the side wall is collected, and then the chamber is cleaned.
The negative electrode composite material for the alkali metal ion battery prepared by the preparation method.
The alkali metal ion battery comprises a positive electrode, a negative electrode, a diaphragm and electrolyte, wherein the negative electrode comprises a negative current collector and a negative material layer coated on the negative current collector, the negative material layer comprises a negative active substance, and the negative active substance is the negative composite material for the alkali metal ion battery. The electrolyte is sodium salt or potassium salt solution. The positive electrode is metallic sodium or metallic potassium.
The negative electrode material layer comprises a negative electrode active material, a binder and a conductive agent in a mass ratio of 75-85:4-12: 2-21. Preferably, the negative electrode material layer is made of a negative electrode active material, a binder and a conductive agent in a mass ratio of 80:10: 10.
The preparation method of the sodium ion battery comprises the following steps:
s1, preparing a positive electrode and a negative electrode;
s2, assembling the positive electrode, the negative electrode and the diaphragm into a battery cell, putting the battery cell into a shell, adding electrolyte, and sealing to obtain the lithium ion battery.
The preparing of the anode in step S1 includes: dissolving a binder in N-methyl pyrrolidone, stirring for 2-6 h to obtain a binder solution, adding the negative active material and a conductive agent into the binder solution, stirring for 6-10h to obtain negative slurry, coating the negative slurry on a copper foil, drying in vacuum at 60-80 ℃ for 8-15 h, and slicing before battery loading. Preferably, the binder is dissolved in N-methyl pyrrolidone and stirred for 6 hours to obtain a binder solution, the negative active material and the conductive agent are added into the binder solution and stirred for 8 hours to obtain negative slurry, the negative slurry is coated on a copper foil and dried in vacuum at 60 ℃ for 8 hours, and the negative slurry is sliced before being filled into a battery.
The binder is dissolved in the N-methyl pyrrolidone and stirred for 6 hours.
The invention has the beneficial effects that:
the carbon-coated bismuth-based composite negative electrode material is prepared by combining the carbon coating and the arc method, and when the negative electrode material is applied to the negative electrode material of a sodium/potassium ion battery, the negative electrode material has high specific capacity and can effectively relieve the volume expansion effect in the charging and discharging processes, so that the negative electrode material has excellent electrochemical performance. And the preparation process is simple and economic, green and environment-friendly, and is suitable for batch production.
The arc discharge method can provide a large amount of energy in a very short time, so that the material is heated and gasified rapidly, and the vapor is condensed rapidly to form nano particles after being diffused out of an arcing center. The invention simultaneously carries out arc discharge reaction on metal and graphite to form the metal nano composite material with carbon coated on the surface, and the carbon material not only can buffer the stress of the metal material when the volume changes in the reaction process and keep the structural integrity of the electrode, but also can be used as a barrier for preventing metal particles from agglomerating.
Compared with the chemical vapor deposition method, the method of the invention is not limited by harsh reaction conditions and low yield; compared with a laser ablation method, the method has lower cost; compared with a wet chemical synthesis method, the method does not have complicated and long reaction process and does not generate more byproducts. The method can synthesize the carbon-coated bismuth-based nano composite material with small size and high reaction activity, is quick, convenient, simple and economical, not only improves the conductivity of the electrode material, can be used as a barrier for blocking the agglomeration of metal particles, but also can effectively slow down the volume expansion effect, thereby further improving the electrochemical performance of the cathode material of the bismuth-based sodium/potassium ion battery.
In conclusion, the preparation process disclosed by the invention is simple in flow, economic in experimental materials, convenient to operate, capable of synthesizing the carbon-coated nano composite material by arc discharge in one step, high in reaction speed, short in experimental period and time-saving and labor-saving. Green and environment-friendly, low in cost and suitable for batch production. No catalyst, solvent or additive is needed to be added in the whole experiment process, and no pollution is caused. The preparation method has strong universality and strong practicability, can synthesize various nano materials by adjusting the types and the proportion of materials, reaction current, atmosphere pressure and other factors, can perform nanocrystallization and coating modification on the materials, and effectively relieves the volume expansion effect of the bismuth-based electrode material in the charging and discharging processes, thereby having excellent electrochemical energy.
Drawings
Fig. 1 is a TEM image of a negative electrode composite material for a sodium ion battery obtained in example 1.
Fig. 2 is an XRD spectrum of the negative electrode composite material for sodium ion battery prepared in example 1.
Fig. 3 is a cycle life chart of the negative electrode composite material for the sodium-ion battery prepared in example 1 as a negative electrode material of the sodium-ion battery, which is cycled for 630 cycles at a current density of 10A/g.
Fig. 4 is a TEM image of the negative electrode composite material for sodium ion battery obtained in example 2.
Fig. 5 is an XRD spectrum of the negative electrode composite for sodium ion battery prepared in example 2.
Fig. 6 is a cycle life chart of the negative electrode composite material for the sodium-ion battery prepared in example 3 as a negative electrode material of the sodium-ion battery, which is cycled 1000 cycles at a current density of 10A/g.
Detailed Description
In order to make the technical problems to be solved, the technical solutions adopted and the technical effects achieved by the present invention easier to understand, the technical solutions of the present invention are clearly and completely described below with reference to specific embodiments.
Example 1
The preparation method of the negative electrode composite material for the sodium-ion battery comprises the following steps:
1) adding 10g of bismuth powder, 4g of graphite and 3g of phenolic resin into a beaker for mixing, then adding 5g of ethyl acetate, and stirring and mixing to obtain paste; then adding the paste into a high-speed stirrer for stirring to change the paste into a powdery mixture;
2) adding the powdery mixture into a stainless steel mold with a cylindrical cavity with the diameter of 5mm, heating to 170 ℃ by a hydraulic press under the continuous pressure of 2MPa, keeping the temperature for 1h, and pressing to obtain the composite rod.
3) And transferring the composite rod into a tube furnace, heating to 800 ℃ at the heating rate of 2 ℃/min, keeping for 6h, and naturally cooling to room temperature to obtain the anode rod.
4) And (3) placing the anode rod serving as an anode and the pure graphite rod serving as a cathode in a sealed cabin of the arc discharge equipment, and sealing the sealed cabin. Vacuumizing to be close to-0.1 MPa, introducing argon to be 0.1MPa, repeatedly pumping and exchanging gas for three times, and introducing argon to the gas pressure of-0.09 MPa. Controlling the distance between the cathode and the anode to be 2mm, starting a circulating water cooling system, adjusting the output current to be 20A, striking an arc, discharging, keeping the atmosphere pressure stable in the discharging process, keeping the discharging time to be 30min, after the discharging is finished, closing cooling water after the cavity is cooled to the room temperature, and collecting soot-like substances settled on the inner wall of the cavity to obtain the carbon-based composite material.
Example 2
The preparation method of the negative electrode composite material for the sodium-ion battery comprises the following steps:
1) adding 8g of bismuth powder, 8g of selenium powder, 5g of graphite and 3g of phenolic resin into a beaker for mixing, then adding 2g of ethyl acetate, and stirring and mixing to obtain paste; then adding the paste into a high-speed stirrer for stirring to change the paste into a powdery mixture;
2) adding the powdery mixture into a stainless steel mold with a cylindrical cavity with the diameter of 5mm, heating to 170 ℃ by a hydraulic press under the continuous pressure of 2MPa, keeping the temperature for 1h, and pressing to obtain the composite rod.
3) And transferring the composite rod into a tube furnace, heating to 800 ℃ at the heating rate of 2 ℃/min, keeping for 6h, and naturally cooling to room temperature to obtain the anode rod.
4) And (3) placing the anode rod serving as an anode and the pure graphite rod serving as a cathode in a sealed cabin of the arc discharge equipment, and sealing the sealed cabin. Vacuumizing to be close to-0.1 MPa, introducing argon to be 0.1MPa, repeatedly pumping and exchanging gas for three times, and introducing argon to the gas pressure of-0.09 MPa. Controlling the distance between the cathode and the anode to be 2mm, starting a circulating water cooling system, adjusting the output current to be 20A, striking an arc, discharging, keeping the atmosphere pressure stable in the discharging process, keeping the discharging time to be 30min, after the discharging is finished, closing cooling water after the cavity is cooled to the room temperature, and collecting soot-like substances settled on the inner wall of the cavity to obtain the carbon-based composite material.
Example 3
The preparation method of the negative electrode composite material for the sodium-ion battery comprises the following steps:
1) adding 4g of bismuth powder, 4g of selenium powder, 2g of titanium dioxide powder, 2g of graphite and 2g of phenolic resin into a beaker for mixing, then adding 1g of ethyl acetate, and stirring and mixing to obtain paste; then adding the paste into a high-speed stirrer for stirring to change the paste into a powdery mixture;
2) adding the powdery mixture into a stainless steel mold with a cylindrical cavity with the diameter of 5mm, heating to 170 ℃ by a hydraulic press under the continuous pressure of 2MPa, keeping the temperature for 1h, and pressing to obtain the composite rod.
3) And transferring the composite rod into a tube furnace, heating to 800 ℃ at the heating rate of 2 ℃/min, keeping for 6h, and naturally cooling to room temperature to obtain the anode rod.
4) And (3) placing the anode rod serving as an anode and the pure graphite rod serving as a cathode in a sealed cabin of the arc discharge equipment, and sealing the sealed cabin. Vacuumizing to be close to-0.1 MPa, introducing argon to be 0.1MPa, repeatedly pumping and exchanging gas for three times, and introducing argon to the gas pressure of-0.09 MPa. Controlling the distance between the cathode and the anode to be 2mm, starting a circulating water cooling system, adjusting the output current to be 20A, striking an arc, discharging, keeping the atmosphere pressure stable in the discharging process, keeping the discharging time to be 30min, after the discharging is finished, closing cooling water after the cavity is cooled to the room temperature, and collecting soot-like substances settled on the inner wall of the cavity to obtain the carbon-based composite material.
Example 4
The preparation method of the negative electrode composite material for the sodium-ion battery is different from that of the embodiment 3 in that 4g of bismuth powder, 2g of selenium powder, 1g of sulfur powder, 1g of tellurium powder, 2g of titanium dioxide powder, 2g of graphite and 2g of phenolic resin are added into a beaker in the step 1) and mixed, then 1.2g of liquid dispersion liquid is added, the liquid dispersion liquid is obtained by mixing ethyl acetate and dibutyl ester according to the mass ratio of 2:1, and stirring and mixing are carried out to obtain paste; then adding the paste into a high-speed stirrer for stirring to change the paste into a powdery mixture;
the rest is the same as in example 3.
Example 5
The preparation method of the negative electrode composite material for the sodium-ion battery in the embodiment is different from that in the embodiment 3 in the following steps 2) to 4):
2) adding the powdery mixture into a stainless steel mold with a cylindrical cavity with the diameter of 5mm, heating to 175 ℃ by a hydraulic press under the continuous pressure of 2MPa, keeping the temperature for 1.5h, and pressing to obtain the composite rod.
3) And transferring the composite rod into a tube furnace, heating to 750 ℃ at the heating rate of 2 ℃/min, keeping for 7h, and naturally cooling to room temperature to obtain the anode rod.
4) And (3) placing the anode rod serving as an anode and the pure graphite rod serving as a cathode in a sealed cabin of the arc discharge equipment, and sealing the sealed cabin. Vacuumizing to be close to-0.1 MPa, introducing argon to be 0.1MPa, repeatedly pumping and exchanging gas for three times, and introducing argon to the gas pressure of-0.09 MPa. Controlling the distance between the cathode and the anode to be 1.2mm, starting a circulating water cooling system, adjusting the output current to be 20A, striking an arc, discharging, keeping the atmosphere pressure stable in the discharging process, keeping the discharging time to be 35min, closing cooling water after the cavity is cooled to the room temperature after discharging is finished, and collecting soot-like substances settled on the inner wall of the cavity.
The rest is the same as in example 3.
Example 6
The preparation method of the sodium-ion battery of the embodiment comprises the following steps:
s1, dissolving a binder polyvinylidene fluoride in N-methyl pyrrolidone, stirring for 6 hours to obtain a binder solution, adding the negative electrode composite material for the sodium-ion battery prepared in any one of the embodiments 1-5 as a negative electrode active material and Keqin black as a conductive agent into the binder solution, stirring for 8 hours, then coating the negative electrode composite material on a copper foil, drying in vacuum at 60 ℃ for 8 hours, and cutting to obtain a negative electrode sheet. The mass ratio of the negative electrode active material to the binder to the conductive agent is 80:10: 10.
and a metal sodium sheet or a metal potassium sheet is used as a positive electrode.
And S2, assembling the sodium-ion battery or the potassium-ion battery according to the positive plate shell, the gasket, the positive plate, the electrolyte, the diaphragm, the negative plate, the gasket, the elastic sheet and the negative plate shell.
The diaphragm is a Gelgard 2400 glass fiber film, and the electrolyte is 1mol L of NaClO4Or KClO4And a solution, wherein the solvent is obtained by mixing propylene carbonate and fluoroethylene carbonate in a volume ratio of 1: 1.
Examples of the experiments
1. Physical Property test
A TEM test and an XRD test were performed on the negative electrode composite material for sodium ion battery obtained in example 1, and the results are shown in fig. 1 and fig. 2, respectively.
TEM and XRD tests were carried out on the negative electrode composite material for sodium-ion battery obtained in example 2, and the results are shown in fig. 4 and 5, respectively.
2. Electrochemical performance test
A sodium ion half-cell was prepared from the negative electrode composite material for sodium ion battery obtained in example 1 by the method described in example 6, and then charged and discharged at a current density of 10A/g, and the cycle curve of the cycle (630 weeks) was as shown in FIG. 3.
A sodium ion half-cell was prepared from the negative electrode composite material for sodium ion battery obtained in example 3 by the method described in example 6, and then charged and discharged at a current density of 10A/g, and the cycle curve of the cycle (1000 cycles) was as shown in FIG. 6.
Claims (10)
1. A preparation method of a negative electrode composite material for an alkali metal ion battery is characterized by comprising the following steps:
1) mixing a bismuth source, graphite, phenolic resin powder and a liquid dispersant to prepare paste, and stirring and scattering the paste to obtain a powdery mixture; the bismuth source is bismuth or bismuth oxide or bismuth chloride;
2) hot-pressing the powdery mixture prepared in the step 1) into a rod-shaped composite rod;
3) sintering the composite rod prepared in the step 2) at the temperature of 600-850 ℃ for 4-8h to obtain an anode rod;
4) taking the anode rod in the step 3) as an anode, taking a graphite rod as a cathode, carrying out arc discharge in an arc discharge device at a current of 15-22A, and collecting the deposit to obtain the graphite electrode.
2. The method for preparing the negative electrode composite material for the alkali metal ion battery according to claim 1, wherein the mass ratio of the bismuth source, the graphite and the phenolic resin powder in the step 1) is 4-10:2-5: 2-3.
3. The method for preparing the negative electrode composite material for the alkali metal ion battery according to claim 1, wherein a complexing agent is further added during mixing of the bismuth source, the graphite, the phenolic resin powder and the liquid dispersing agent in the step 1), wherein the complexing agent is at least one of selenium powder, sulfur powder, tellurium powder and phosphorus powder; the mass ratio of the complexing agent to the bismuth source is 4-8: 4-10.
4. The method for preparing the negative electrode composite material for the alkali metal ion battery according to claim 1, wherein titanium dioxide is further added when the bismuth source, graphite, phenolic resin powder and the liquid dispersant are mixed in the step 1), and the mass ratio of the titanium dioxide to the bismuth source is 2-3: 4-10.
5. The method for preparing the negative electrode composite material for the alkali metal ion battery according to claim 1, wherein the pressure in the hot pressing in the step 2) is 0.1 to 10MPa, the temperature in the hot pressing is 50 to 270 ℃, and the time for the hot pressing is 1 to 1.5 hours.
6. The method for preparing the negative electrode composite material for the alkali metal ion battery as recited in claim 1, wherein the temperature rise rate in the tubular furnace in the step 3) to 600-850 ℃ is 1-2 ℃/min.
7. The method for preparing a negative electrode composite material for an alkali metal ion battery according to claim 1, wherein the distance between the anode and the cathode in step 4) is 1 to 2 mm.
8. The method for preparing the negative electrode composite material for the alkali metal ion battery according to claim 1, wherein the arc discharge time in the step 4) is 30 to 45 min.
9. The negative electrode composite material for alkali metal ion batteries, which is produced by the method for producing a negative electrode composite material for alkali metal ion batteries according to claim 1.
10. An alkali metal ion battery comprising a positive electrode, a negative electrode, a separator, and an electrolyte, wherein the negative electrode comprises a negative electrode current collector and a negative electrode material layer coated on the negative electrode current collector, the negative electrode material layer comprises a negative electrode active material, and the negative electrode active material is the negative electrode composite material for the alkali metal ion battery according to claim 9.
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Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105312086A (en) * | 2014-08-04 | 2016-02-10 | 西北大学 | Preparation method for carbon-coated bismuth nano composite material |
| CN105810947A (en) * | 2016-04-29 | 2016-07-27 | 深圳博磊达新能源科技有限公司 | Aluminum ion battery anode material, electrode and aluminum ion battery |
| CN107611376A (en) * | 2017-08-22 | 2018-01-19 | 哈尔滨工程大学 | A kind of preparation method of graphene parcel silicon particle composite |
| CN108199032A (en) * | 2018-01-20 | 2018-06-22 | 西南大学 | The preparation of the hollow bismuth simple substance of carbon-coated nano and its alkaline battery application |
| CN110357227A (en) * | 2019-07-09 | 2019-10-22 | 中南大学 | A kind of method of selective Electro Sorb halide ion in composite salt waste water |
| CN111235696A (en) * | 2020-01-21 | 2020-06-05 | 南京航空航天大学 | Bismuth-phosphorus-sulfur/carbon composite nanofiber negative electrode material for sodium ion battery, preparation method of bismuth-phosphorus-sulfur/carbon composite nanofiber negative electrode material and sodium ion battery |
| CN111769272A (en) * | 2020-07-28 | 2020-10-13 | 广西师范大学 | Bi @ C hollow nanosphere composite material and preparation method and application thereof |
| CN112234173A (en) * | 2020-10-14 | 2021-01-15 | 昆明理工大学 | Carbon-coated silicon nano-particles and preparation method and application thereof |
| CN113571682A (en) * | 2021-07-29 | 2021-10-29 | 广东工业大学 | Bismuth/carbon composite material and preparation method and application thereof |
| CN113839038A (en) * | 2021-08-12 | 2021-12-24 | 山东大学 | MOF-derived Bi @ C nano composite electrode material and preparation method thereof |
-
2022
- 2022-01-05 CN CN202210003633.2A patent/CN114335484A/en active Pending
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105312086A (en) * | 2014-08-04 | 2016-02-10 | 西北大学 | Preparation method for carbon-coated bismuth nano composite material |
| CN105810947A (en) * | 2016-04-29 | 2016-07-27 | 深圳博磊达新能源科技有限公司 | Aluminum ion battery anode material, electrode and aluminum ion battery |
| CN107611376A (en) * | 2017-08-22 | 2018-01-19 | 哈尔滨工程大学 | A kind of preparation method of graphene parcel silicon particle composite |
| CN108199032A (en) * | 2018-01-20 | 2018-06-22 | 西南大学 | The preparation of the hollow bismuth simple substance of carbon-coated nano and its alkaline battery application |
| CN110357227A (en) * | 2019-07-09 | 2019-10-22 | 中南大学 | A kind of method of selective Electro Sorb halide ion in composite salt waste water |
| CN111235696A (en) * | 2020-01-21 | 2020-06-05 | 南京航空航天大学 | Bismuth-phosphorus-sulfur/carbon composite nanofiber negative electrode material for sodium ion battery, preparation method of bismuth-phosphorus-sulfur/carbon composite nanofiber negative electrode material and sodium ion battery |
| CN111769272A (en) * | 2020-07-28 | 2020-10-13 | 广西师范大学 | Bi @ C hollow nanosphere composite material and preparation method and application thereof |
| CN112234173A (en) * | 2020-10-14 | 2021-01-15 | 昆明理工大学 | Carbon-coated silicon nano-particles and preparation method and application thereof |
| CN113571682A (en) * | 2021-07-29 | 2021-10-29 | 广东工业大学 | Bismuth/carbon composite material and preparation method and application thereof |
| CN113839038A (en) * | 2021-08-12 | 2021-12-24 | 山东大学 | MOF-derived Bi @ C nano composite electrode material and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 李希龙: "电弧放电法制备钠离子电池铋基负极材料", 万方平台在线出版硕士论文, pages 27 - 57 * |
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