CN112018368A - Nano alloy type negative electrode material and preparation method thereof - Google Patents
Nano alloy type negative electrode material and preparation method thereof Download PDFInfo
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Abstract
The invention provides a preparation method of a nano alloy type negative electrode material, which comprises the following steps: A) mixing a positive electrode material capable of generating an electrochemical reaction for extracting alkali metal ions with an electrolyte to obtain a positive electrode solution; mixing an alloy type negative electrode material which is subjected to alloying reaction with alkali metal with electrolyte to obtain negative electrode solution; B) assembling the anode solution and the cathode solution into an alkali metal ion flow battery; C) and adjusting the alkali metal ion flow battery to enable the anode material and the alloy type cathode material to generate charge-discharge electrochemical reaction, so as to obtain the nano alloy type cathode material. The application also provides a preparation method of the nano alloy type anode material. The two methods take the alkali metal ion flow battery as a synthesis means to obtain the nano-sized alloyed cathode material or the nano-sized alloyed anode material which is different from the original structure.
Description
Technical Field
The invention relates to the technical field of alkali metal ion battery cathode materials, in particular to a nano alloy type cathode material and a preparation method thereof.
Background
In lithium ion batteries, sodium ion batteries, and potassium ion batteries, the alloying negative electrode material is a metal and an alloy thereof, a mesophase compound, and a composite thereof, which can undergo an alloying reaction with an alkali metal (M) (M ═ K, Na, and Li). It is reported that alkali metals react with many metals (e.g., silicon, germanium, tin, lead, magnesium, aluminum, antimony, calcium, silver, zinc, cadmium, bismuth, platinum, lead, arsenic, mercury, etc.) at normal temperature, and the charge-discharge mechanism is essentially alloying and reverse alloying. Generally, the theoretical specific capacity and charge density of the alloying type negative electrode material are far higher than those of the embedding type negative electrode material; the lithium storage specific capacities of representative stannum and silicon respectively reach 900mAh g-1And 3600mAh g-1. Meanwhile, the lithium intercalation potential of the material is high, the deposition of lithium is difficult to occur under the condition of large-current charge and discharge, and lithium dendrite cannot be generated to cause short circuit of the battery, so that the material has important significance for high-power devices. However, in the reversible reaction process of the alloy material and alkali metal to form a compound, the volume change rate of the material is close to 300 percent, and the high volume change directly causes the reversibility of the electrode to be reduced; in the long circulation process, the active electrode material is easily powdered, the cohesiveness with the conductive current collector is failed, and further the conductivity is reduced to generate capacity loss. And the active electrolyte membrane on the surface of the metal simple substance reacts with the electrolyte under the condition of low voltage to generate and dissolve continuously, so that the electrolyte is consumed continuously, and the performance of the battery is adversely affected. Therefore, the control of the larger volume change rate of the metal simple substance in the charge-discharge cycle process is the key for improving the electrode performance. Researchers find that the use of nanostructure-scale alloyed negative electrode materials helps to reduce the volume change rate during cycling and improve the electrochemical performance of the electrode material.
The synthesis of functional materials based on electrochemical processes is a novel preparation method, and has received some attention in recent years, but reports are few. The high and erect people of Stanford university in America do little work, and an electrochemical regulation and control method is adopted to adjust the reactivity, the structural performance and the like of catalyst materials such as molybdenum disulfide, lithium iron phosphate and the like (adv. Mater.2018,30,1800978; ACS Nano,2014,8: 4940-; the synthesized material is mostly used as a catalyst for electrocatalytic hydrogen production or oxygen production reaction. In addition, no report is available for synthesizing the anode material of the alkali metal ion battery by using an electrochemical process.
Disclosure of Invention
The invention aims to provide a preparation method of a nano alloy type cathode material or a nano alloy type anode material, which can prepare a nano alloy type cathode material or an alloy type anode material, and can obviously reduce the volume change rate in the circulation process and improve the electrochemical performance of the electrode material when being applied to an alkali metal ion battery.
In view of the above, the present application provides a method for preparing a nano alloy type negative electrode material, which includes the following steps:
A) mixing an alkali metal ion battery anode material capable of generating an alkali metal de-intercalation electrochemical reaction with an electrolyte to obtain an anode solution;
mixing an alkali metal ion battery alloy type negative electrode material capable of generating alloying reaction with alkali metal with electrolyte to obtain negative electrode solution;
B) assembling the positive electrode solution and the negative electrode solution into an alkali metal ion full flow battery;
C) and adjusting the alkali metal ion full flow battery to enable the alkali metal ion battery anode material and the alkali metal ion battery alloy type cathode material to generate electrochemical reaction of charging and discharging, so as to obtain the nano alloy type cathode material.
The application also provides a preparation method of the nano alloy type anode material, which comprises the following steps:
A) mixing an alkali metal ion battery alloy type anode material capable of generating alloying reaction with alkali metal with electrolyte to obtain anode solution;
taking alkali metal as a negative electrode material;
B) assembling the positive electrode solution and the negative electrode material into an alkali metal ion semi-flow battery;
C) and adjusting the alkali metal ion semi-flow battery to enable the alloy type anode material of the alkali metal ion battery and alkali metal to generate electrochemical reaction of charging and discharging, so as to obtain the nano alloy type anode material.
Preferably, the cathode material is selected from one or more of cobalt oxide, manganese oxide, nickel oxide and iron phosphate oxide of alkali metals.
Preferably, the alloy-type negative electrode material is selected from one of silicon, tin, germanium, lead, magnesium, aluminum, antimony, calcium, silver, zinc, cadmium, bismuth, platinum, arsenic and mercury, an alloy formed by the above elements, a mesophase compound formed by the above elements, or a composite formed by the above elements.
Preferably, the content of the cathode material in the cathode solution is 0.1-99.9%, and the content of the anode material in the anode solution is 0.1-99.9%.
Preferably, step B) further includes one or both of a conductive agent and a redox pair when assembled into the alkali metal ion full flow battery;
the conductive agent is selected from any one or more of SUPER-P, KS-6, conductive graphite, carbon nano tubes, graphene, carbon fiber VGCF and the like; the redox couple is selected from Fe3+/Fe2+、I3-/I-、Br3-/Br-、Cu2+/Cu、O2/OH-And S4 2-/S2One or more of (a).
Preferably, the alkali metal ion battery alloy type positive electrode material is selected from one of silicon, tin, germanium, lead, magnesium, aluminum, antimony, calcium, silver, zinc, cadmium, bismuth, platinum, arsenic and mercury, an alloy formed by the above elements, a mesophase compound formed by the above elements, or a composite formed by the above elements.
Preferably, step B) further comprises one or both of a conductive agent and a redox couple when assembled into the alkali metal ion semi-flow battery;
the conductive agent is selected from one or more of SUPER-P, KS-6, conductive graphite, carbon nano tube, graphene, carbon fiber VGCF and the likeSeed growing; the redox couple is selected from Fe3+/Fe2+、I3-/I-、Br3-/Br-、Cu2+/Cu、O2/OH-And S4 2-/S2One or more of (a).
Preferably, the conditions for regulating the alkali metal ion full flow battery or the alkali metal ion half flow battery are as follows: the charging and discharging cycle process is complete, the charging and discharging are carried out firstly, the charging and discharging voltage range is 0-4.5V, the charging and discharging current density is 0.01C-20C, the cycle frequency is 1-1000, and the flow speed of the anode liquid or the cathode liquid is 1-1000 ml/min.
The application provides a preparation method of a nano alloy type cathode material and a preparation method of a nano alloy type anode material, wherein the alloy type cathode material or the alloy type anode material is used as a raw material, an alkali metal ion flow battery is utilized, and the raw material is subjected to structural change and volume change in an electrochemical reaction, so that the structural change and the size reduction of the raw material are realized, and the nano alloy type nano cathode material or the alloy type nano anode material with the nano size different from the original structure is finally obtained; the cathode material or the anode material is used as the cathode material of the alkali metal ion battery again, so that the volume change rate in the circulation process can be obviously reduced, and the electrochemical performance of the electrode material is improved.
Drawings
FIG. 1 is a scanning electron microscope image of elemental silicon as a negative electrode material used in step (2) of example 1;
FIG. 2 is a high-power scanning electron microscope image of elemental silicon as a negative electrode material used in step (2) in example 1;
FIG. 3 is a scanning electron microscope image of the final product, namely, the nano-silicon material obtained in example 1;
FIG. 4 shows the cycle performance of the final product, i.e., the nano-silicon material obtained in example 1;
FIG. 5 is a scanning electron microscope image of the final product, namely, the nano germanium material obtained in example 2;
fig. 6 shows the cycle performance of the final product, namely nano germanium material obtained in example 2.
Detailed Description
For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the invention, and not to limit the scope of the claims.
The applicant has found through research that: the volume of the active substance in the alloy type negative electrode material or the alloy type positive electrode material undergoes expansion and contraction after multiple alkali metal electrochemical reactions, so that particles are broken and pulverized, and the particle size is reduced; meanwhile, the structural morphology of the active substance is changed due to negative reactions such as decomposition of the electrolyte on the surface of the active substance, and the active substance after alkali metal cycle is removed is collected again, so that a novel material with the size and the structure different from those of the initial material can be obtained. Based on the point, the original size of the alloy type cathode material can be reduced by using an electrochemical reaction, the structural appearance of the alloy type cathode material is changed, a novel cathode material or a novel anode material with a nano scale different from the original structure is prepared, and the volume effect in the charge and discharge process is weakened; therefore, the nano-scale alloying negative electrode material is prepared by utilizing the alkali metal ion flow battery based on the alkali metal extraction electrochemical reaction. Specifically, the method comprises the following steps:
A) mixing an alkali metal ion battery anode material capable of generating an alkali metal de-intercalation electrochemical reaction with an electrolyte to obtain an anode solution;
mixing an alkali metal ion battery alloy type negative electrode material capable of generating alloying reaction with alkali metal with electrolyte to obtain negative electrode solution;
B) assembling the positive electrode solution and the negative electrode solution into an alkali metal ion full flow battery;
C) and adjusting the alkali metal ion full flow battery to enable the alkali metal ion battery anode material and the alkali metal ion battery alloy type cathode material to generate electrochemical reaction of charging and discharging, so as to obtain the nano alloy type cathode material.
Reference herein to alkali metals and their related references primarily to lithium, sodium and potassium.
In the process of preparing the nano alloy type negative electrode material, the method firstly needs to prepare a positive electrode solution and a negative electrode solution of the alkali metal ion flow battery; the alkali metal ion full flow battery described herein is well known to those skilled in the art. The alkali metal ion full flow battery may be specifically selected from a semi-solid alkali metal ion full flow battery or a redox alkali metal ion full flow battery. For the positive electrolyte of the alkali metal ion flow battery, the positive electrode material can be selected from one or more of cobalt oxide, manganese oxide, nickel oxide and iron phosphate oxide of alkali metal; taking a lithium ion flow battery as an example, the positive electrode material can be one or more of lithium cobaltate, lithium manganate, lithium nickelate, lithium iron phosphate, lithium nickel cobalt manganate, lithium nickel cobalt aluminate and high nickel material; taking a potassium ion flow battery as an example, the positive electrode material can be selected from one or more of potassium cobaltate, potassium manganate, potassium nickelate, potassium iron phosphate, potassium nickel cobalt manganate and potassium nickel cobalt aluminate; taking a sodium ion flow battery as an example, the positive electrode material can be selected from one or more of sodium cobaltate, sodium manganate, sodium nickelate, sodium iron phosphate, sodium nickel cobalt manganate and sodium nickel cobalt aluminate. The content of the positive electrode material in the positive electrode solution is 0.1-99.9%, and in a specific embodiment, the content of the positive electrode material in the positive electrode solution is 10-50%.
The negative electrode material is an alloy type negative electrode material which can generate alloying reaction with alkali metal, and the alloy type negative electrode material is selected from one of silicon, tin, germanium, lead, magnesium, aluminum, antimony, calcium, silver, zinc, cadmium, bismuth, platinum, arsenic and mercury, an alloy formed by the elements, a mesophase compound formed by the elements or a compound formed by the elements; in a specific embodiment, the alloy type negative electrode material is selected from tin, germanium or silicon. The content of the negative electrode material in the negative electrode solution is 0.1-99.9%, and in a specific embodiment, the content of the negative electrode material in the negative electrode solution is 10-50%.
In the positive electrode solution and the negative electrode solution, the electrolyte is independently selected from an aqueous electrolyte or a non-aqueous electrolyte; the nonaqueous electrolyte includes any one of the following three components in combination (1) a solvent: cyclic carbonates (PC, EC);chain carbonates (DEC, DMC, EMC); carboxylic acid esters (MF, MA, EA, MA, MP, etc.) for dissolving metal salts; (2) lithium salt: LiPF6、LiClO4、LiBF4、LiAsF6Etc.; sodium salt: NaPF6、NaClO4、NaBF4、NaAsF6Etc., potassium salt: KPF6、KClO4、KBF4、KAsF6Etc.; (3) additive: film forming additive, conductive additive, flame retardant additive, overcharge protection additive and control of H in electrolyte2Additives with O and HF content, additives for improving low-temperature performance and multifunctional additives.
After the anode solution and the cathode solution are obtained, the anode solution and the cathode solution are assembled with a battery reactor, a liquid pump, a sealing pipeline and other components to form the alkali metal ion full flow battery; the diaphragm of the alkali metal ion full flow battery is well known to those skilled in the art, and is specifically selected from polyolefin films such as polyethylene and polypropylene, fluorine-containing polymer diaphragms such as polyvinylidene fluoride, cellulose diaphragms, polyimide diaphragms, polyester diaphragms or diaphragms made of other non-conductive polymer materials; glass fiber non-woven fabric, synthetic fiber non-woven fabric, ceramic fiber paper or other microporous inorganic non-metallic material diaphragms; a polymer ceramic composite diaphragm; a solid electrolyte separator. In the process of assembling the alkali metal ion full flow battery, a conductive agent or a redox couple can be selectively added according to different types of alkali metal ion full flow batteries; wherein the conductive agent is selected from any one or more of SUPER-P, KS-6, conductive graphite, carbon nano tube, graphene, carbon fiber VGCF and the like; the redox couple is selected from Fe3+/Fe2+、I3-/I-、Br3-/Br-、Cu2+/Cu、O2/OH-And S4 2-/S2One or more of (a).
And after the alkali metal ion full flow battery is assembled, adjusting the alkali metal ion full flow battery to enable the positive electrode material and the alloy type negative electrode material to generate charge and discharge electrochemical reactions, wherein the alloy type negative electrode material is embedded with alkali metal ions during charge, and the alloy type negative electrode material is separated from the alkali metal ions during discharge, so that the nano-chemical alloy type negative electrode material is obtained. More specifically, the conditions for regulating the alkali metal ion flow battery are as follows: the charge-discharge cycle process is complete, the charge-discharge voltage range is 0-4.5V, the charge-discharge current density is 0.01-20C, the cycle frequency is 1-1000, and the flow speed of the anode liquid or the cathode liquid is 1-1000 ml/min. In a specific embodiment, the number of charge and discharge cycles is 1 to 100, the charge and discharge current density is 0.1 to 2C, the voltage range is 0.005 to 4.0V, and the flow rate of the positive electrode solution or the negative electrode solution is 30 to 100 ml/min.
According to the difference of the alkali metal ion flow battery, the application also provides a preparation method of the nano alloy type anode material, which comprises the following steps:
A) mixing an alkali metal ion battery alloy type anode material capable of generating alloying reaction with alkali metal with electrolyte to obtain anode solution;
taking alkali metal as a negative electrode material;
B) assembling the positive electrode solution and the negative electrode material into a lithium ion semi-flow battery;
C) and adjusting the lithium ion semi-flow battery to enable the alkali metal ion battery alloy type anode material and alkali metal to generate electrochemical reaction of charging and discharging, so as to obtain the nano alloy type anode material.
In the process of preparing the nano alloy type anode material, an alkali metal ion semi-flow battery is adopted, namely, alkali metal is used as a cathode material, an alloy type material capable of generating alloying reaction with the alkali metal is used as an anode, and the alloy type anode material is subjected to lithium removal in the discharging process. The alloying positive electrode material is selected from one of silicon, tin, germanium, lead, magnesium, aluminum, antimony, calcium, silver, zinc, cadmium, bismuth, platinum, arsenic and mercury, an alloy formed by the elements, a mesophase compound formed by the elements or a compound formed by the elements; in a particular embodiment, the alloyed positive electrode material is selected from tin.
The electrolyte is well known to those skilled in the art, and the electrolyte described in the above scheme is exemplified, and the present application is not particularly limited. Also included in the anolyte is one or both of a conductive agent and a redox couple as described above. The alkali metal ion semi-flow battery is selected from a semi-solid alkali metal ion semi-flow battery or a redox alkali metal ion semi-flow battery.
The adjusting conditions in the charging and discharging processes of the alkali metal ion semi-flow battery are as follows: the charging and discharging cycle process is complete, the charging and discharging are carried out firstly, the charging and discharging voltage range is 0-4.5V, the charging and discharging current density is 0.01C-20C, the cycle frequency is 1-1000, and the flow speed of the anode solution is 1-1000 ml/min.
The size of the nano alloy type cathode material or the nano alloy type anode material prepared by the method can reach 1 nm-1000 nm.
According to the invention, the alloy type cathode material or the alloy type anode material is prepared into the nano alloy type cathode material or the nano alloy type anode material based on electrochemical reaction in the form of the alkali metal ion flow battery, the alkali metal ion flow battery has various forms, the storage capacity of active substances is large, the product quality can reach the kilogram level, and the large-scale amplification production is favorably realized; the method can effectively reduce the original size of the alloy type cathode material, realize the nano conversion preparation of the material, contribute to reducing the volume change rate of the alloy type cathode material in the circulation process and improve the electrochemical performance of the material; the preparation method can be orderly regulated and controlled, and the structural morphology of the material, including a crystal structure, an electronic structure, a space conformation, a specific surface area, interface binding energy, size and the like, can be further regulated and controlled by changing parameters such as a battery form, voltage, current, cycle number and the like. On the other hand, the preparation method is suitable for all alloy type alkali metal ion cathode materials capable of generating electrochemical reaction, and has wide application range.
In order to further understand the present invention, the following will explain the nano alloy type negative electrode material provided by the present invention in detail with reference to the following examples, and the scope of the present invention is not limited by the following examples.
Example 1 semisolid lithium ion full flow battery as reactor
Step 1) preparing lithium cobaltate serving as a positive electrode material and conductive carbon black serving as a conductive agent into a positive electrode material suspension of the lithium ion flow battery with conventional electrolyte according to the mass ratio of 10% to 1%;
step 2) taking simple substance silicon as a negative electrode material and conductive carbon black as a conductive agent, and preparing the simple substance silicon and conventional electrolyte into a lithium ion flow battery negative electrode material suspension according to the mass ratio of 10% and 1% respectively;
step 3) transferring the positive suspension and the negative suspension into a storage tank respectively, connecting various components such as a battery reactor, a liquid pump, a sealed pipeline and the like, and assembling the semi-solid lithium ion full flow battery;
step 4) adjusting a hydraulic pump of the semisolid lithium ion full flow battery to enable the positive electrode liquid and the negative electrode liquid to circulate at the speed of 20mL/min, setting the charging and discharging voltage range to be 2-4.0V, performing charging and discharging circulation at the current density of 0.1C for 10 times, enabling the positive electrode active material lithium cobaltate to perform a lithium removal reaction during charging, and enabling the negative electrode material silicon to perform lithium intercalation to generate a lithium silicide alloy (Li) during chargingxSi), during discharge, the lithium silicide alloy is subjected to lithium removal and is converted into simple substance silicon again, and the pulverization of particles simultaneously occurs due to the volume effect; the final discharge is carried out for many times to the lowest voltage, so that the electrochemical reaction is fully carried out on the silicon cathode, and the nano-crystallization of the particles is realized;
step 5) post-treatment: and after the charge and discharge cycle is completed, separating solid matters in the negative storage tank from corresponding suspension by standing or centrifuging, and washing and drying to obtain the required nano silicon material.
As shown in fig. 1 and 2, the elemental silicon material adopted in step (2) of example 1 is micron-sized and has a particle size of about 2 to 10 microns, and the final product obtained in step (5) is nano-sized and has a particle size of about 30 to 50 nanometers, as shown in fig. 3, so that it can be inferred that size nanocrystallization can be realized after charge and discharge cycles of the semi-solid lithium ion full flow battery, and the micron silicon is converted into nano silicon; FIG. 4 shows that the capacity of the nano silicon material still has 583mAh/g after 50 cycles, and the capacity of the micron silicon material quickly decays to 148mAh/g after 10 cycles, which shows that the lithium ion battery cathode material has more stable cycle performance than the micron silicon.
Example 2 a redox lithium ion full flow battery was used as a reactor,
step 1) placing 100 g of lithium iron phosphate anode material in an anode storage tank, adding 200 g of carbonate electrolyte, taking ferrocene/bromoferrocene as redox mediator molecules, and controlling the concentration of the mediator molecules in the electrolyte to be 20 mM;
step 2) placing 50 g of germanium metal microparticle anode material in an anode storage tank, adding 100 g of the same carbonate electrolyte, taking ferrocene/bromoferrocene as redox mediator molecules, wherein the concentration of the mediator molecules in the electrolyte is 20 mM;
step 3) connecting the positive and negative electrode storage tanks with various components such as a battery reactor, a liquid pump, a sealed pipeline and the like to form a complete redox lithium ion full flow battery;
step 4) adjusting a hydraulic pump of the redox lithium ion full flow battery to enable the positive electrode liquid and the negative electrode liquid to circulate at a speed of 50mL/min, setting a charging and discharging voltage range to be 2-4.5V, performing charging and discharging circulation at a current density of 0.2C, and circulating for 20 times, wherein a lithium removal electrochemical reaction is performed on a positive electrode lithium iron phosphate material during charging, a lithium insertion reaction is performed on a negative electrode material to generate a germanium-lithium alloy, the discharging process is just opposite, the germanium-lithium alloy in the negative electrode is removed from lithium to form a germanium simple substance again, and the size is reduced due to the volume effect; after 20 cycles, the size of the germanium metal is gradually nanocrystallized;
step 5) post-treatment: and after the charge-discharge cycle is completed, separating the solid matters in the cathode storage tank from the corresponding suspension by standing or centrifuging, and washing and drying to obtain the nano germanium metal simple substance.
The shape of the final product obtained in the step (5) in the embodiment 2 is shown in fig. 5, the final product has a nano size, and the particle size is about 10-100 nanometers, so that the nano size can be realized after the charge and discharge cycles of the lithium ion flow battery, and the micro germanium is converted into nano germanium; FIG. 6 shows that the capacity of the nano germanium material is 1092mAh/g after the nano germanium material circulates for 100 circles, which shows that the nano germanium material has stable circulation performance.
Example 3 semi-solid lithium ion full flow battery as reactor
Step 1) preparing lithium manganate serving as a positive electrode material and conductive carbon black serving as a conductive agent, and conventional electrolyte into a lithium ion flow battery positive electrode material suspension according to the mass ratio of 10% to 1% respectively;
step 2) taking 50 g of tin microparticles as a negative electrode material, 2 g of conductive carbon black KB300 and 200 g of 1M LiPF6Preparing the electrolyte (EC and DMC mass ratio is 1:1) into negative pole liquid;
step 3) transferring and assembling the two materials into a lithium ion flow battery device with a storage tank, a hydraulic pump and a filter press, connecting completely, and adjusting the hydraulic pump to enable the positive and negative electrode suspensions to circulate at the speed of 40 mL/min;
step 4) setting the charging and discharging voltage range to be 2-3.8V, performing charging and discharging circulation at the current density of 0.5C, circulating for 50 times, performing lithium intercalation reaction on tin metal during discharging to generate tin-lithium alloy, and removing lithium from the tin-lithium alloy during charging to form a tin simple substance, wherein the size is reduced due to the volume effect and even nanocrystallization; the metal tin is fully subjected to electrochemical reaction through multiple cycles, so that nanocrystallization is realized;
step 5) post-treatment: and after the charge-discharge cycle is completed, separating the solid matters in the cathode storage tank from the corresponding suspension by standing or centrifuging, and washing and drying to obtain the nano tin metal simple substance.
Example 4 lithium ion semi-flow battery as reactor
Step 1) with 10 grams of tin metal, 2 grams of conductive carbon black KB300 and 200 grams of 1M LiPF6Preparing the electrolyte (EC and DMC mass ratio is 1:1) into positive solution;
step 2) taking lithium metal with the thickness of 0.5 millimeter and the size of 10 square centimeters as a negative electrode material and taking Celgard2000 as a diaphragm;
step 3) transferring and assembling the two materials into a lithium ion flow battery device with a storage tank, a hydraulic pump and a pressure filter, connecting completely, and adjusting the hydraulic pump to enable the positive electrode liquid to circulate at a speed of 31 mL/min;
step 4) setting the charging and discharging voltage range to be 0.005-3V, discharging at the current density of 0.5C, carrying out lithium intercalation reaction on tin metal to generate tin-lithium alloy, and removing lithium from the tin-lithium alloy during charging to form a tin simple substance, wherein the size is reduced or even nanocrystallized due to the volume effect; the metal tin is fully subjected to electrochemical reaction through multiple cycles, so that nanocrystallization is realized;
step 5) post-treatment: and after the charge-discharge cycle is completed, separating the solid matters in the cathode storage tank from the corresponding suspension by standing or centrifuging, and washing and drying to obtain the nano tin metal simple substance.
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (9)
1. A preparation method of a nano alloy type negative electrode material comprises the following steps:
A) mixing an alkali metal ion battery anode material capable of generating an alkali metal de-intercalation electrochemical reaction with an electrolyte to obtain an anode solution;
mixing an alkali metal ion battery alloy type negative electrode material capable of generating alloying reaction with alkali metal with electrolyte to obtain negative electrode solution;
B) assembling the positive electrode solution and the negative electrode solution into an alkali metal ion full flow battery;
C) and adjusting the alkali metal ion full flow battery to enable the alkali metal ion battery anode material and the alkali metal ion battery alloy type cathode material to generate electrochemical reaction of charging and discharging, so as to obtain the nano alloy type cathode material.
2. A preparation method of a nano alloy type anode material comprises the following steps:
A) mixing an alkali metal ion battery alloy type anode material capable of generating alloying reaction with alkali metal with electrolyte to obtain anode solution;
taking alkali metal as a negative electrode material;
B) assembling the positive electrode solution and the negative electrode material into an alkali metal ion semi-flow battery;
C) and adjusting the alkali metal ion semi-flow battery to enable the alloy type anode material of the alkali metal ion battery and alkali metal to generate electrochemical reaction of charging and discharging, so as to obtain the nano alloy type anode material.
3. The method according to claim 1, wherein the positive electrode material is selected from one or more of cobalt oxide, manganese oxide, nickel oxide, and iron phosphate oxide of alkali metal.
4. The method according to claim 1, wherein the alloy-type negative electrode material is selected from one of silicon, tin, germanium, lead, magnesium, aluminum, antimony, calcium, silver, zinc, cadmium, bismuth, platinum, arsenic, and mercury, an alloy of the foregoing elements, a mesophase compound of the foregoing elements, or a composite of the foregoing elements.
5. The preparation method according to claim 1, wherein the content of the positive electrode material in the positive electrode solution is 0.1% to 99.9%, and the content of the negative electrode material in the negative electrode solution is 0.1% to 99.9%.
6. The production method according to claim 1, wherein in step B), one or both of a conductive agent and a redox pair are further included in assembling the alkali metal ion full flow battery;
the conductive agent is selected from SUPER-P, KS-6, conductive stoneAny one or more of ink, carbon nanotubes, graphene, carbon fiber VGCF, and the like; the redox couple is selected from Fe3+/Fe2+、I3-/I-、Br3-/Br-、Cu2+/Cu、O2/OH-And S4 2-/S2One or more of (a).
7. The method according to claim 2, wherein the alkali metal ion battery alloy-type positive electrode material is selected from one of silicon, tin, germanium, lead, magnesium, aluminum, antimony, calcium, silver, zinc, cadmium, bismuth, platinum, arsenic, and mercury, an alloy of the foregoing elements, a mesophase compound of the foregoing elements, or a composite of the foregoing elements.
8. The method according to claim 2, wherein step B) further comprises one or both of a conductive agent and a redox couple during assembly into the alkali metal ion semi-flow battery;
the conductive agent is selected from any one or more of SUPER-P, KS-6, conductive graphite, carbon nano tubes, graphene, carbon fiber VGCF and the like; the redox couple is selected from Fe3+/Fe2+、I3-/I-、Br3-/Br-、Cu2+/Cu、O2/OH-And S4 2-/S2One or more of (a).
9. The production method according to claim 1 or 2, characterized in that the conditions that the alkali metal ion full-flow battery or the alkali metal ion semi-flow battery regulates are: the charging and discharging cycle process is complete, the charging and discharging are carried out firstly, the charging and discharging voltage range is 0-4.5V, the charging and discharging current density is 0.01C-20C, the cycle frequency is 1-1000, and the flow speed of the anode liquid or the cathode liquid is 1-1000 ml/min.
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