CN110571500B - Lithium-sulfur semi-flow battery - Google Patents

Lithium-sulfur semi-flow battery Download PDF

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CN110571500B
CN110571500B CN201910880904.0A CN201910880904A CN110571500B CN 110571500 B CN110571500 B CN 110571500B CN 201910880904 A CN201910880904 A CN 201910880904A CN 110571500 B CN110571500 B CN 110571500B
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lithium
sulfur
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lithium metal
electrolyte
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CN110571500A (en
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张义永
张英杰
李雪
董鹏
孟奇
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Kunming University of Science and Technology
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M12/00—Hybrid cells; Manufacture thereof
    • H01M12/08—Hybrid cells; Manufacture thereof composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

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Abstract

The invention discloses a lithium-sulfur semi-flow battery, which comprises a sulfur flow positive electrode area, a lithium metal negative electrode area and a diaphragm; the liquid sulfur positive region comprises a working electrode and lithium polysulfide catholyte; the working electrode comprises an active material, a conductive agent, a binder and a current collector; the active material is Ni/C composite material, pt/C composite material or Pt 3 A Ni/C composite material; the lithium polysulfide cathode electrolyte consists of lithium polysulfide dissolved in lithium sulfur electrolyte; the lithium metal negative electrode region comprises a lithium metal negative electrode and a lithium sulfur electrolyte, and the lithium metal negative electrode is lithium metal or lithium metal alloy; the diaphragm is a single ion film; the lithium-sulfur semi-flow battery has high energy density, high power density and long service life, and can be widely used as a power supply of various machines such as an electric vehicle or a hybrid electric vehicle and also as a large-scale energy storage device of a power grid.

Description

Lithium-sulfur semi-flow battery
Technical Field
The invention relates to the field of electrochemical energy, in particular to a lithium-sulfur semi-flow battery with high energy density, high power density and long cycle life.
Background
In recent decades, the use of solar energy, tidal energy, and wind energy has increased, and electric vehicles with low carbon dioxide emissions have been spreading. Therefore, in order to effectively utilize renewable energy, the development of high-performance, safe, inexpensive, and environmentally friendly energy conversion and storage systems is imperative. Preferred among these energy storage systems are lithium ion batteries and supercapacitors. Lithium ion batteries are common electrochemical devices for storing electrical energy. However, despite their commercial success, lithium ion batteries fail to meet the high power requirements needed for applications such as power tools, electric vehicles, and efficient storage devices for renewable energy sources. In contrast, supercapacitors, in addition to providing higher energy densities than conventional dielectric capacitors, also show promise for high power systems because they can instantaneously provide higher power densities than batteries. However, the energy density of supercapacitors is still insufficient for new applications requiring high energy and high power density.
To overcome these disadvantages, research on lithium ion batteries has focused on electrode material improvements, for example, the use of silicon negative electrodes and lithium rich positive electrodes. However, these materials themselves suffer from several drawbacks, including low first-pass coulombic efficiency, unsatisfactory rate performance, poor cycle life, poor thermal characteristics, and significant voltage decay. In fact, alternative battery systems, such as lithium air batteries, lithium sulfur batteries, and sodium/magnesium ion batteries, have proven to be superior to lithium ion batteries in terms of energy/power density, safety, and cost. However, these systems also have their own drawbacks. For example, during the charging and discharging processes of the lithium-sulfur battery, due to the dissolution shuttling of the intermediate, the utilization rate of the active material of the battery is reduced and the cycle life is shortened; meanwhile, the rate performance of the battery is poor due to poor conductivity of active substances, namely sulfur and lithium sulfide, and in order to improve the conductivity, a large amount of conductive additives are required to be added, so that the content of the active substances is reduced, the volume energy density of the battery is low, and the high energy density of the lithium-sulfur battery is difficult to exert. Therefore, in order to solve these problems, a new class of lithium-sulfur flow battery systems has recently been proposed. The system includes the use of a working electrode having electrocatalytic activity, a lithium polysulfide catholyte, a separator, and a negative region including a lithium metal negative electrode and a conventional lithium sulfur electrolyte. Although the lithium-sulfur semi-flow battery has high energy density and power density, the problems of catalytic activity and stability of the working electrode and selectivity of the separator must be solved to realize commercial application thereof.
Disclosure of Invention
The invention provides a lithium-sulfur semi-flow battery with high energy density, high power density and long service life, which comprises a sulfur flow positive electrode area, a lithium metal negative electrode area and a diaphragm.
The flowing sulfur positive region includes a working electrode, a lithium polysulfide catholyte.
The working electrode comprises an active material capable of catalyzing the conversion of lithium polysulfide, a conductive agent, a binder and a current collector; the mass ratio of the active material capable of catalyzing the conversion of lithium polysulfide to the conductive agent to the binder is 8; the conductive agent and the binder are common products of commercial batteries, preferably Super p is used as the conductive agent, and preferably polyvinylidene fluoride (PVDF) is used as the binder; the current collector is one of common current collectors such as aluminum foil, stainless steel mesh and carbon paper or self-supporting, and preferably, the stainless steel mesh is selected.
The active material capable of catalyzing the conversion of lithium polysulfide is Ni/C composite material, pt/C composite material or Pt 3 Ni, pt-loaded Ni/C composite material or the like 3 A conductive carrier of Ni.
The lithium polysulfide cathode electrolyte is formed by dissolving lithium polysulfide in lithium sulfur electrolyte, and the concentration of the lithium polysulfide is 0.1-2 mol/L, preferably 1mol/L; the solvent of the lithium-sulfur electrolyte is R (CH) 2 CH 2 O) n-R 'wherein n =1-6,R and R' is methyl or ethyl, the solute is lithium difluorooxalato borate, lithium bistrifluoromethylsulfonylimide, lithium difluorosulfonylimide, lithium difluorophosphate or lithium hexafluorophosphate, and the concentration of the lithium sulfur electrolyte is 1mol/L.
The lithium metal negative electrode region comprises a lithium metal negative electrode and lithium sulfur electrolyte, the lithium metal negative electrode is lithium metal or lithium metal alloy, and the lithium metal alloy is lithium tin alloy, lithium silicon alloy or lithium copper alloy; the solvent of the lithium-sulfur electrolyte is R (CH) 2 CH 2 O) n-R 'wherein n =1-6,R and R' is methyl or ethyl, the solute is lithium difluorooxalato borate, lithium bistrifluoromethylsulfonylimide, lithium difluorosulfonylimide, lithium difluorophosphate or lithium hexafluorophosphate, and the concentration of the lithium sulfur electrolyte is 1mol/L.
The diaphragm comprises one of a single ion film such as PP or PE and a three-layer film such as PP/PE/PP.
The preparation method of the Ni/C composite material comprises the following specific steps:
(1) Ultrasonically treating the C conductive carrier and deionized water for 1~5 hours to obtain a carbon-based carrier dispersion liquid with the concentration of 1-10mg/mL; the C conductive carrier is one of graphene, super p, carbon black, acetylene black, CNT and the like;
(2) Adding nickel acetate or nickel nitrate into the carbon-based carrier dispersion liquid in the step (1) according to the mass ratio of C to Ni of 5-15, and performing ultrasonic treatment for 1~5 hours to obtain a mixed dispersion liquid;
(3) Rapidly freezing the mixed dispersion liquid in the step (2) by using liquid nitrogen, and freeze-drying by using a freeze dryer to obtain mixed powder;
(4) And (3) under the protection of Ar gas, placing the mixed powder in the step (3) in a tube furnace, heating to 700-900 ℃ at the heating rate of 5 ℃/min, calcining for 1~3 hours, and naturally cooling to obtain the Ni/C composite material.
The preparation method of the Pt/C composite material is the same as that of the Ni/C composite material, and nickel acetate or nickel nitrate in the step (2) is replaced by platinum acetate or platinum nitrate.
The Pt is 3 The preparation method of the Ni/C composite material comprises the following specific steps:
(1) Adding the C conductive carrier into a round-bottom flask containing DMF, and performing ultrasonic treatment for 1~5 hours to obtain a carbon-based carrier dispersion liquid with the concentration of 1-10mg/mL; the C conductive carrier is one of graphene, super p, carbon black, acetylene black, CNT and the like;
(2) Mixing platinum diacetone (Pt (acac) 2 ) Nickel diacetone (Ni (acac) 2 ) Push button Pt (acac) 2 :Ni(acac) 2 Adding C into the carbon-based carrier dispersion liquid in the step (1) according to the mass ratio of 8 to 24, wherein C is the following component (C);
(3) Heating the mixed dispersion liquid in the step (2) in a constant-temperature water bath at 150 to 170 ℃, and reacting for 20 to 24 hours;
(4) Centrifugally separating the product obtained in the step (3) to obtain Pt 3 A Ni/C composite material.
The preparation method of the working electrode comprises the following specific steps:
(1) Mixing 80 parts by weight of an active material capable of catalyzing the conversion of lithium polysulfide and 10 parts by weight of a conductive agent and grinding to obtain mixed powder;
(2) Stirring and mixing the mixed powder in the step (1) and 10 parts by weight of binder solution, and coating the mixed slurry on a current collector; coating the slurry to the thickness of a current collector preferably 10 to 500 micrometers, and drying in vacuum at 60 ℃ for 10 to 24 hours to remove the solvent to obtain the working electrode.
The lithium-sulfur half-flow battery is assembled by taking a working electrode and lithium polysulfide cathode electrolyte as a liquid sulfur positive electrode region, taking a lithium metal negative electrode and the lithium sulfur electrolyte as a lithium metal negative electrode region and a diaphragm together according to the assembly mode of a commercial liquid flow battery, and then the lithium-sulfur half-flow battery is obtained; the electrochemical redox of lithium polysulfide occurs in the liquid flow sulfur positive electrode area, the stripping/deposition of lithium occurs in the lithium metal negative electrode area, the lithium polysulfide cathode electrolyte in the liquid flow sulfur positive electrode area also plays a role in providing active substance lithium polysulfide, the electrolyte between the working electrode and the counter electrode mainly plays a role in transferring charges by conducting lithium ions, meanwhile, solute lithium salt has good solubility and ionic conductivity in the electrolyte, which has important influence on the working temperature, specific energy, cycle efficiency, safety performance and the like of the battery, the intermediate diaphragm separates the positive electrode active substance and the negative electrode active substance of the battery, only allows lithium ions to pass through, prevents any electron flow between the positive electrode and the negative electrode from directly passing through, and avoids the short circuit of the battery; the ion flow has as low a resistance as possible when passing through it, and it has a high energy density and power density.
The invention has the beneficial effects that:
1. the lithium-sulfur semiliquid flow battery has the performances of high energy density, high power density and long service life, can be used as a secondary battery for a driving power supply in mobile information instruments such as mobile phones and notebook computers, and can be widely used as a power supply of various machines such as electric vehicles or hybrid electric vehicles.
2. The lithium-sulfur semi-flow battery shows strong energy and power density and excellent cycle performance, the lithium-sulfur semi-flow battery utilizes the working electrode to catalyze the mutual conversion among lithium polysulfides, and meanwhile, the conversion among the lithium polysulfides is liquid-liquid reaction, so that the utilization rate and the reaction rate of active substances are improved, and the sulfur active substances have high theoretical specific capacity (such as sulfur: 1675 mAh/g), therefore, the lithium-sulfur semi-flow battery can overcome the challenges brought by the traditional lithium-sulfur battery, and finally realizes high capacity, good rate characteristic and excellent cycle performance, thereby being used as an advanced energy storage device.
3. The method has low implementation cost and large-scale application potential.
Drawings
FIG. 1 is a schematic diagram of the structure of a lithium-sulfur semi-flow battery of example 1;
FIG. 2 shows Pt in example 9 3 SEM image of Ni/C composite material;
FIG. 3 shows Pt in example 9 3 A charge-discharge curve diagram of a lithium-sulfur semi-flow battery with a Ni/C composite material as a working electrode;
FIG. 4 shows Pt in example 9 3 And (3) a cycle performance diagram of the lithium-sulfur semi-flow battery with the Ni/C composite material as the working electrode.
Detailed Description
The invention will be further illustrated by the following examples in conjunction with the drawings, but it will be understood that the examples are for the purpose of illustrating embodiments of the invention and that the scope of protection is not limited by the examples described without departing from the scope of the subject matter of the invention.
Additional objects and advantages of the invention will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. In the following description, "%" is based on mass unless otherwise specified.
Example 1
A lithium-sulfur semi-flow battery with high energy density, high power density and long service life comprises a sulfur flow positive electrode area, a lithium metal negative electrode area and a diaphragm; the positive liquid sulfur area comprises a working electrode and lithium polysulfide catholyte; the working electrode comprises an active material capable of catalyzing the conversion of lithium polysulfide, a conductive agent, a binder and a current collector; the mass ratio of the active material capable of catalyzing the conversion of lithium polysulfide, the conductive agent and the binder is 8; the conductive agent and the binder are common products of commercial batteries, preferably Super p is used as the conductive agent, and preferably polyvinylidene fluoride (PVDF) is used as the binder; the current collector is a stainless steel mesh; the active material capable of catalyzing the conversion of lithium polysulfide is a Ni/C composite material; lithium polysulfide cathode electrolyte is prepared by dissolving lithium polysulfide in lithium sulfur electrolyteThe concentration of lithium polysulfide is 1mol/L; the lithium metal negative electrode region comprises a lithium metal negative electrode and a lithium sulfur electrolyte, the lithium metal negative electrode is lithium metal, and the diaphragm is a three-layer porous membrane made of PP/PE/PP materials; the solvent of the lithium-sulfur electrolyte of the embodiment is represented by the formula R (CH) 2 CH 2 O) n-R 'wherein n =1,R and R' are both methyl, the solute is lithium difluorooxalato borate, and the concentration of the lithium sulfur electrolyte is 1mol/L.
The preparation process of the lithium-sulfur semi-flow battery of the embodiment specifically comprises the following steps:
A. the preparation method of the Ni/C composite material comprises the following specific steps:
(1) Adding the C conductive carrier graphene dispersion liquid (3 wt%) into a beaker filled with deionized water, and carrying out ultrasonic treatment for 1 hour to obtain a carbon-based carrier dispersion liquid with the concentration of 1 mg/mL;
(2) Adding nickel nitrate into the carbon-based carrier dispersion liquid obtained in the step (1) according to the mass ratio of C to Ni of 5:1, and performing ultrasonic treatment for 5 hours to obtain a mixed dispersion liquid;
(3) Rapidly freezing the mixed dispersion liquid in the step (2) by using liquid nitrogen, and freeze-drying by using a freeze dryer to obtain mixed powder;
(4) Placing the mixed powder in the step (3) in a tube furnace under the protection of Ar gas, heating to 800 ℃ at the speed of 5 ℃/min, calcining for 2 hours, and naturally cooling to obtain a Ni/C composite material;
B. the preparation method of the working electrode comprises the following specific steps:
(1) Mixing and grinding 80 parts by weight of the active material Ni/C composite material capable of catalyzing the conversion of lithium polysulfide prepared in the step A and 10 parts by weight of conductive agent Super p to obtain mixed powder;
(2) Stirring and mixing the mixed powder obtained in the step (1) and 10 parts by weight of a binder polyvinylidene fluoride (PVDF), and coating the mixed slurry on a current collector; coating the slurry until the thickness of the current collector is 10 microns, and performing vacuum drying at 60 ℃ for 24 hours to remove the solvent to obtain a working electrode;
C. and (2) preparing the lithium-sulfur semi-flow battery, as shown in figure 1, assembling the working positive electrode obtained in the step (B) and the lithium polysulfide catholyte which are used as a liquid sulfur positive electrode area together, assembling a lithium metal negative electrode and the lithium sulfur electrolyte which are used as a lithium metal negative electrode area together with a diaphragm according to the assembly mode of the commercial flow battery, and superposing the working electrode, the catholyte, the PP/PE/PP three-layer porous membrane, the lithium sulfur electrolyte and the lithium metal negative electrode in sequence in a glove box in an argon atmosphere to obtain the lithium-sulfur semi-flow battery.
The performance of the battery is tested in a battery test system, the charge-discharge cut-off voltage is 1.8V to 2.6V, and the charge-discharge current density is 0.50mA/cm.
Example 2
A lithium-sulfur semi-flow battery with high energy density, high power density and long service life comprises a sulfur flow positive electrode area, a lithium metal negative electrode area and a diaphragm; the liquid sulfur positive region comprises a working electrode and lithium polysulfide catholyte; the working electrode comprises an active material capable of catalyzing the conversion of lithium polysulfide, a conductive agent, a binder and a current collector; the mass ratio of the active material capable of catalyzing the conversion of lithium polysulfide, the conductive agent and the binder is 8; the conductive agent and the binder are common products of commercial batteries, preferably Super p is used as the conductive agent, and preferably polyvinylidene fluoride (PVDF) is used as the binder; the current collector is an aluminum foil; the active material capable of catalyzing the conversion of lithium polysulfide is a Pt/C composite material; the lithium polysulfide cathode electrolyte is formed by dissolving lithium polysulfide in lithium sulfur electrolyte, and the concentration of the lithium polysulfide is 1mol/L; the lithium metal negative electrode region comprises a lithium metal negative electrode and a lithium sulfur electrolyte, the lithium metal negative electrode is lithium metal, and the diaphragm is a three-layer porous membrane made of PP/PE/PP materials; the solvent of the lithium-sulfur electrolyte of the embodiment is represented by the formula R (CH) 2 CH 2 O) n-R 'wherein n =2,R and R' are both ethyl, the solute is lithium bistrifluoromethylsulfonyl imide, and the concentration of the lithium sulfur electrolyte is 1mol/L.
The preparation process of the lithium-sulfur semi-flow battery of the embodiment comprises the following specific steps:
A. the preparation method of the Ni/C composite material comprises the following specific steps:
(1) Adding the C conductive carrier graphene dispersion liquid (3 wt%) into a beaker filled with deionized water, and carrying out ultrasonic treatment for 2 hours to obtain a carbon-based carrier dispersion liquid with the concentration of 5 mg/mL;
(2) Adding nickel acetate into the carbon-based carrier dispersion liquid in the step (1) according to the mass ratio of C to Ni of 10;
(3) Rapidly freezing the mixed dispersion liquid in the step (2) by using liquid nitrogen, and freeze-drying by using a freeze dryer to obtain mixed powder;
(4) Placing the mixed powder in the step (3) in a tube furnace under the protection of Ar gas, heating to 700 ℃ at the speed of 5 ℃/min, calcining for 3 hours, and naturally cooling to obtain a Ni/C composite material;
B. the preparation method of the working electrode comprises the following specific steps:
(1) Mixing 80 parts by weight of the active material Ni/C composite material capable of catalyzing the conversion of lithium polysulfide prepared in the step A and 10 parts by weight of conductive agent Super p, and grinding to obtain mixed powder;
(2) Stirring and mixing the mixed powder obtained in the step (1) and 10 parts by weight of a binder polyvinylidene fluoride (PVDF), and coating the mixed slurry on a current collector; coating the slurry until the thickness of the current collector is 30 microns, and performing vacuum drying at 60 ℃ for 24 hours to remove the solvent to obtain a working electrode;
C. and C, preparing the lithium-sulfur semi-flow battery, namely using the working anode obtained in the step B and the lithium polysulfide catholyte together as a liquid sulfur anode region, using the lithium metal cathode and the lithium sulfur electrolyte as a lithium metal cathode region, assembling the lithium metal cathode and the lithium sulfur electrolyte together with a diaphragm into the battery according to the assembly mode of the commercial liquid flow battery, and superposing the working electrode, the catholyte, the PP/PE/PP three-layer porous membrane, the lithium sulfur electrolyte and the lithium metal cathode in sequence in a glove box in an argon atmosphere to obtain the lithium-sulfur semi-flow battery.
The performance of the battery is tested in a battery test system, the charge-discharge cut-off voltage is 1.8V to 2.6V, and the charge-discharge current density is 0.50mA/cm.
Example 3
A lithium-sulfur semi-flow battery with high energy density, high power density and long service life comprises a sulfur flow positive electrode area, a lithium metal negative electrode area and a diaphragm; the positive liquid sulfur area comprises a working electrode and lithium polysulfide catholyte; working electrode bagThe lithium polysulfide conversion catalyst comprises an active material capable of catalyzing the conversion of lithium polysulfide, a conductive agent, a binder and a current collector; the mass ratio of the active material capable of catalyzing the conversion of lithium polysulfide, the conductive agent and the binder is 8; the conductive agent and the binder are common products of commercial batteries, preferably Super p is used as the conductive agent, and preferably polyvinylidene fluoride (PVDF) is used as the binder; the current collector is carbon paper; the active material capable of catalyzing the conversion of lithium polysulfide is a Ni/C composite material; the lithium polysulfide cathode electrolyte is formed by dissolving lithium polysulfide in lithium sulfur electrolyte, and the concentration of the lithium polysulfide is 0.1mol/L; the lithium metal negative electrode region comprises a lithium metal negative electrode and lithium sulfur electrolyte, the lithium metal negative electrode is a lithium tin alloy (Li0.9Sn0.1), and the diaphragm is a three-layer porous diaphragm (PP/PE/PP); the solvent of the lithium-sulfur electrolyte of the embodiment is represented by the formula R (CH) 2 CH 2 O) n-R 'wherein n =6,R is ethyl, R' is methyl, the solute is lithium bis (fluorosulfonyl) imide, and the concentration of the lithium sulfur electrolyte is 1mol/L.
The preparation process of the lithium-sulfur semi-flow battery of the embodiment specifically comprises the following steps:
A. the preparation method of the Ni/C composite material comprises the following specific steps:
(1) Adding the C conductive carrier graphene dispersion liquid (3 wt%) into a beaker filled with deionized water, and carrying out ultrasonic treatment for 5 hours to obtain a carbon-based carrier dispersion liquid with the concentration of 10 mg/mL;
(2) Adding nickel acetate into the carbon-based carrier dispersion liquid obtained in the step (1) according to the mass ratio of C to Ni of 15;
(3) Rapidly freezing the mixed dispersion liquid in the step (2) by using liquid nitrogen, and freeze-drying by using a freeze dryer to obtain mixed powder;
(4) Placing the mixed powder in the step (3) in a tube furnace under the protection of Ar gas, heating to 900 ℃ at the speed of 5 ℃/min, calcining for 1 hour, and naturally cooling to obtain a Ni/C composite material;
B. the preparation method of the working electrode comprises the following specific steps:
(1) Mixing and grinding 80 parts by weight of the active material Ni/C composite material capable of catalyzing the conversion of lithium polysulfide prepared in the step A and 10 parts by weight of conductive agent Super p to obtain mixed powder;
(2) Stirring and mixing the mixed powder obtained in the step (1) and 10 parts by weight of a binder polyvinylidene fluoride (PVDF), and coating the mixed slurry on a current collector; coating the slurry until the thickness of the current collector is 50 microns, and performing vacuum drying at 60 ℃ for 10 hours to remove the solvent to obtain a working electrode;
C. and C, preparing the lithium-sulfur semi-flow battery, namely using the working positive electrode obtained in the step B and the lithium polysulfide catholyte together as a liquid sulfur positive electrode area, using the lithium metal negative electrode and the lithium sulfur electrolyte as a lithium metal negative electrode area, assembling the lithium metal negative electrode and the lithium sulfur electrolyte together with a diaphragm into the battery according to the assembly mode of the commercial liquid flow battery, and stacking the working electrode, the catholyte, the three-layer porous diaphragm (PP/PE/PP), the lithium sulfur electrolyte and the lithium metal negative electrode in sequence in a glove box in an argon atmosphere to obtain the lithium-sulfur semi-flow battery.
The performance of the battery is tested in a battery test system, the cut-off voltage of charge and discharge is 1.8V to 2.6V, and the current density of charge and discharge is 0.50mA cm -2 。
Example 4
A lithium-sulfur semi-flow battery with high energy density, high power density and long service life comprises a sulfur flow positive electrode area, a lithium metal negative electrode area and a diaphragm; the liquid sulfur positive region comprises a working electrode and lithium polysulfide catholyte; the working electrode comprises an active material capable of catalyzing the conversion of lithium polysulfide, a conductive agent, a binder and a current collector; the mass ratio of the active material capable of catalyzing the conversion of lithium polysulfide, the conductive agent and the binder is 8; the conductive agent and the binder are common products of commercial batteries, preferably Super p is used as the conductive agent, and preferably polyvinylidene fluoride (PVDF) is used as the binder; the current collector is a stainless steel mesh; the active material capable of catalyzing the conversion of lithium polysulfide is a Pt/C composite material; the lithium polysulfide cathode electrolyte is formed by dissolving lithium polysulfide into lithium sulfur electrolyte, and the concentration of the lithium polysulfide is 1mol/L; the lithium metal negative electrode region comprises a lithium metal negative electrode and lithium sulfur electrolyte, the lithium metal negative electrode is lithium silicon alloy (Li0.9Si0.1), and the diaphragm is a three-layer porous diaphragm (PP/PE/PP); the solvent of the lithium-sulfur electrolyte of the embodiment is represented by the formula R (CH) 2 CH 2 Polyethers of O) n-R', whichIn the formula, n =6,R and R' are both methyl, the solute is lithium hexafluorophosphate, and the concentration of the lithium sulfur electrolyte is 1mol/L.
The preparation process of the lithium-sulfur semi-flow battery of the embodiment specifically comprises the following steps:
A. the preparation method of the Pt/C composite material comprises the following specific steps:
(1) Adding the C conductive carrier graphene dispersion liquid (3 wt%) into a beaker filled with deionized water, and performing ultrasonic treatment for 3 hours to obtain a carbon-based carrier dispersion liquid with the concentration of 10 mg/mL;
(2) Adding platinum acetate into the carbon-based carrier dispersion liquid obtained in the step (1) according to the mass ratio of C to Pt of 15;
(3) Rapidly freezing the mixed dispersion liquid in the step (2) by using liquid nitrogen, and freeze-drying by using a freeze dryer to obtain mixed powder;
(4) Placing the mixed powder in the step (3) in a tube furnace under the protection of Ar gas, heating to 800 ℃ at the speed of 5 ℃/min, calcining for 2 hours, and naturally cooling to obtain a Pt/C composite material;
B. the preparation method of the working electrode comprises the following specific steps:
(1) Mixing and grinding 80 parts by weight of the active material Pt/C composite material capable of catalyzing the conversion of lithium polysulfide prepared in the step A and 10 parts by weight of conductive agent Super p to obtain mixed powder;
(2) Stirring and mixing the mixed powder obtained in the step (1) and 10 parts by weight of adhesive polyvinylidene fluoride (PVDF), and coating the mixed slurry on a current collector; coating the slurry until the thickness of the current collector is 30 microns, and performing vacuum drying at 60 ℃ for 15 hours to remove the solvent to obtain a working electrode;
C. and C, preparing the lithium-sulfur semi-flow battery, namely using the working anode obtained in the step B and lithium polysulfide catholyte together as a liquid sulfur anode region, using a lithium metal cathode and lithium sulfur electrolyte as a lithium metal cathode region, assembling the lithium metal cathode and the lithium sulfur electrolyte together with a diaphragm into the battery according to the assembly mode of the commercial liquid flow battery, and stacking the working electrode, the catholyte, the three-layer porous diaphragm (PP/PE/PP), the lithium sulfur electrolyte and the lithium metal cathode in sequence in a glove box in an argon atmosphere to obtain the lithium-sulfur semi-flow battery.
The performance of the battery is tested in a battery test system, the charge-discharge cut-off voltage is 1.8V to 2.6V, and the charge-discharge current density is 0.50mA/cm.
Example 5
A lithium-sulfur semi-flow battery with high energy density, high power density and long service life comprises a sulfur flow positive electrode area, a lithium metal negative electrode area and a diaphragm; the positive liquid sulfur area comprises a working electrode and lithium polysulfide catholyte; the working electrode comprises an active material capable of catalyzing the conversion of lithium polysulfide, a conductive agent, a binder and a current collector; the mass ratio of the active material capable of catalyzing the conversion of lithium polysulfide, the conductive agent and the binder is 8; the conductive agent and the binder are common products of commercial batteries, preferably Super p is used as the conductive agent, and preferably polyvinylidene fluoride (PVDF) is used as the binder; the current collector is a stainless steel mesh; the active material capable of catalyzing the conversion of lithium polysulfide is a Pt/C composite material; the lithium polysulfide cathode electrolyte is formed by dissolving lithium polysulfide in lithium sulfur electrolyte, and the concentration of the lithium polysulfide is 2mol/L; the lithium metal negative electrode region comprises a lithium metal negative electrode and lithium sulfur electrolyte, the lithium metal negative electrode is a lithium copper alloy (Li0.9Cu0.1), and the diaphragm is a three-layer porous diaphragm (PP/PE/PP); the solvent of the lithium-sulfur electrolyte of the embodiment is represented by the formula R (CH) 2 CH 2 O) n-R 'wherein n =2,R and R' are both ethyl, the solute is lithium bistrifluoromethylsulfonimide, and the concentration of the lithium sulfur electrolyte is 1mol/L.
The preparation process of the lithium-sulfur semi-flow battery of the embodiment comprises the following specific steps:
A. the preparation method of the Pt/C composite material comprises the following specific steps:
(1) Adding the C conductive carrier acetylene black dispersion liquid (3 wt%) into a beaker filled with deionized water, and carrying out ultrasonic treatment for 1 hour to obtain a carbon-based carrier dispersion liquid with the concentration of 4 mg/mL;
(2) Adding platinum nitrate into the carbon-based carrier dispersion liquid in the step (1) according to the mass ratio of C to Pt of 10;
(3) Rapidly freezing the mixed dispersion liquid in the step (2) by using liquid nitrogen, and freeze-drying by using a freeze dryer to obtain mixed powder;
(4) Placing the mixed powder in the step (3) in a tube furnace under the protection of Ar gas, heating to 900 ℃ at the speed of 5 ℃/min, calcining for 1 hour, and naturally cooling to obtain a Pt/C composite material;
B. the preparation method of the working electrode comprises the following specific steps:
(1) Mixing and grinding 80 parts by weight of the Pt/C composite material which is the active material and can catalyze the conversion of lithium polysulfide and is prepared in the step A and 10 parts by weight of Super p which is a conductive agent to obtain mixed powder;
(2) Stirring and mixing the mixed powder obtained in the step (1) and 10 parts by weight of a binder polyvinylidene fluoride (PVDF), and coating the mixed slurry on a current collector; coating the slurry until the thickness of the current collector is 10 microns, and performing vacuum drying at 60 ℃ for 12 hours to remove the solvent to obtain a working electrode;
C. and C, preparing the lithium-sulfur semi-flow battery, namely using the working positive electrode obtained in the step B and the lithium polysulfide catholyte together as a liquid sulfur positive electrode area, using the lithium metal negative electrode and the lithium sulfur electrolyte as a lithium metal negative electrode area, assembling the lithium metal negative electrode and the lithium sulfur electrolyte together with a diaphragm into the battery according to the assembly mode of the commercial liquid flow battery, and stacking the working electrode, the catholyte, the three-layer porous diaphragm (PP/PE/PP), the lithium sulfur electrolyte and the lithium metal negative electrode in sequence in a glove box in an argon atmosphere to obtain the lithium-sulfur semi-flow battery.
The performance of the battery is tested in a battery test system, the charge-discharge cut-off voltage is 1.8V to 2.6V, and the charge-discharge current density is 0.50mA/cm.
Example 6
A lithium-sulfur semi-flow battery with high energy density, high power density and long service life comprises a sulfur flow positive electrode area, a lithium metal negative electrode area and a diaphragm; the liquid sulfur positive region comprises a working electrode and lithium polysulfide catholyte; the working electrode comprises an active material capable of catalyzing the conversion of lithium polysulfide, a conductive agent, a binder and a current collector; the mass ratio of the active material capable of catalyzing the conversion of lithium polysulfide, the conductive agent and the binder is 8; the conductive agent and the binder are common products of commercial batteries, preferably Super p is used as the conductive agentSelecting polyvinylidene fluoride (PVDF) as a binder; the current collector is a stainless steel mesh; the active material capable of catalyzing the conversion of lithium polysulfide is a Pt/C composite material; the lithium polysulfide cathode electrolyte is formed by dissolving lithium polysulfide in lithium sulfur electrolyte, and the concentration of the lithium polysulfide is 1mol/L; the lithium metal negative electrode region comprises a lithium metal negative electrode and lithium sulfur electrolyte, the lithium metal negative electrode is lithium metal, and the diaphragm is a three-layer porous diaphragm (PP/PE/PP); the solvent of the lithium-sulfur electrolyte of the embodiment is represented by the formula R (CH) 2 CH 2 O) n-R 'wherein n =5,R is methyl, R' is ethyl, the solute is lithium difluorophosphate, and the concentration of the lithium sulfur electrolyte is 1mol/L.
The preparation process of the lithium-sulfur semi-flow battery of the embodiment specifically comprises the following steps:
A. the preparation method of the Pt/C composite material comprises the following specific steps:
(1) Adding the C conductive carrier graphene dispersion liquid (3 wt%) into a beaker filled with deionized water, and carrying out ultrasonic treatment for 5 hours to obtain a carbon-based carrier dispersion liquid with the concentration of 1 mg/mL;
(2) Adding platinum nitrate into the carbon-based carrier dispersion liquid obtained in the step (1) according to the mass ratio of C to Pt of 5:1, and performing ultrasonic treatment for 1 hour to obtain a mixed dispersion liquid;
(3) Rapidly freezing the mixed dispersion liquid in the step (2) by using liquid nitrogen, and freeze-drying by using a freeze dryer to obtain mixed powder;
(4) Placing the mixed powder in the step (3) in a tube furnace under the protection of Ar gas, heating to 700 ℃ at a speed of 5 ℃/min, calcining for 3 hours, and naturally cooling to obtain a Pt/C composite material;
B. the preparation method of the working electrode comprises the following specific steps:
(1) Mixing and grinding 80 parts by weight of the active material Pt/C composite material capable of catalyzing the conversion of lithium polysulfide prepared in the step A and 10 parts by weight of conductive agent Super p to obtain mixed powder;
(2) Stirring and mixing the mixed powder obtained in the step (1) and 10 parts by weight of adhesive polyvinylidene fluoride (PVDF), and coating the mixed slurry on a current collector; coating the slurry until the thickness of the current collector is 500 micrometers, and vacuum-drying at 60 ℃ for 24 hours to remove the solvent to obtain a working electrode;
C. and C, preparing the lithium-sulfur semi-flow battery, namely using the working positive electrode obtained in the step B and the lithium polysulfide catholyte together as a liquid sulfur positive electrode area, using the lithium metal negative electrode and the lithium sulfur electrolyte as a lithium metal negative electrode area, assembling the lithium metal negative electrode and the lithium sulfur electrolyte together with a diaphragm into the battery according to the assembly mode of the commercial liquid flow battery, and stacking the working electrode, the catholyte, the three-layer porous diaphragm (PP/PE/PP), the lithium sulfur electrolyte and the lithium metal negative electrode in sequence in a glove box in an argon atmosphere to obtain the lithium-sulfur semi-flow battery.
The performance of the battery is tested in a battery test system, the charge-discharge cut-off voltage is 1.8V to 2.6V, and the charge-discharge current density is 0.50mA/cm.
Example 7
A lithium-sulfur semi-flow battery with high energy density, high power density and long service life comprises a sulfur flow positive electrode area, a lithium metal negative electrode area and a diaphragm; the liquid sulfur positive region comprises a working electrode and lithium polysulfide catholyte; the working electrode comprises an active material capable of catalyzing the conversion of lithium polysulfide, a conductive agent, a binder and a current collector; the mass ratio of the active material capable of catalyzing the conversion of lithium polysulfide, the conductive agent and the binder is 8; the conductive agent and the binder are common products of commercial batteries, preferably Super p is used as the conductive agent, and preferably polyvinylidene fluoride (PVDF) is used as the binder; the current collector is a stainless steel mesh; the active material capable of catalyzing the conversion of lithium polysulfide is Pt 3 A Ni/C composite material; the lithium polysulfide cathode electrolyte is formed by dissolving lithium polysulfide into lithium sulfur electrolyte, and the concentration of the lithium polysulfide is 1mol/L; the lithium metal negative electrode region comprises a lithium metal negative electrode and lithium sulfur electrolyte, the lithium metal negative electrode is lithium metal, and the diaphragm is a three-layer porous diaphragm (PP/PE/PP); the solvent of the lithium-sulfur electrolyte of the embodiment is represented by the formula R (CH) 2 CH 2 O) n-R 'wherein n =2,R and R' are both ethyl, the solute is lithium bistrifluoromethylsulfonimide, and the concentration of the lithium sulfur electrolyte is 1mol/L.
The preparation process of the lithium-sulfur semi-flow battery of the embodiment comprises the following specific steps:
A、Pt 3 preparation method of Ni/C composite materialThe method comprises the following specific steps:
(1) Adding a C conductive carrier Super p with the weight of 10mg into a round-bottom flask containing 10mL of DMF, and performing ultrasonic treatment for 1 hour to obtain a carbon-based carrier dispersion liquid with the concentration of 1 mg/mL;
(2) Platinum diacetylacetonate (Pt (acac) 2 ) Nickel diacetone (Ni (acac) 2 ) Push button Pt (acac) 2 :Ni(acac) 2 Adding C into the carbon-based carrier dispersion liquid in the step (1) according to the mass ratio of 8;
(3) Heating the mixed dispersion liquid in the step (2) in a constant-temperature water bath at 150 ℃, and reacting for 24 hours;
(4) Centrifugally separating the product obtained in the step (3) to obtain Pt 3 A Ni/C composite material;
B. the preparation method of the working electrode comprises the following specific steps:
(1) 80 parts by weight of active material Pt which is prepared in the step A and can catalyze the conversion of lithium polysulfide 3 Mixing the Ni/C composite material and 10 parts by weight of conductive agent Super p, and grinding to obtain mixed powder;
(2) Stirring and mixing the mixed powder obtained in the step (1) and 10 parts by weight of a binder polyvinylidene fluoride (PVDF) solution, and coating the mixed slurry on a current collector; coating the slurry until the thickness of the current collector is 50 microns, and performing vacuum drying at 60 ℃ for 24 hours to remove the solvent to obtain a working electrode;
C. and C, preparing the lithium-sulfur semi-flow battery, namely using the working positive electrode obtained in the step B and the lithium polysulfide catholyte together as a liquid sulfur positive electrode area, using the lithium metal negative electrode and the lithium sulfur electrolyte as a lithium metal negative electrode area, assembling the lithium metal negative electrode and the lithium sulfur electrolyte together with a diaphragm into the battery according to the assembly mode of the commercial liquid flow battery, and stacking the working electrode, the catholyte, the three-layer porous diaphragm (PP/PE/PP), the lithium sulfur electrolyte and the lithium metal negative electrode in sequence in a glove box in an argon atmosphere to obtain the lithium-sulfur semi-flow battery.
The performance of the battery is tested in a battery test system, the charge-discharge cut-off voltage is 1.8V to 2.6V, and the charge-discharge current density is 0.50mA/cm.
Example 8
A lithium-sulfur semi-flow battery with high energy density, high power density and long service life comprises a sulfur flow positive electrode area, a lithium metal negative electrode area and a diaphragm; the positive liquid sulfur area comprises a working electrode and lithium polysulfide catholyte; the working electrode comprises an active material capable of catalyzing the conversion of lithium polysulfide, a conductive agent, a binder and a current collector; the mass ratio of the active material capable of catalyzing the conversion of lithium polysulfide, the conductive agent and the binder is 8; the conductive agent and the binder are common products of commercial batteries, preferably Super p is used as the conductive agent, and preferably polyvinylidene fluoride (PVDF) is used as the binder; the current collector is a stainless steel mesh; the active material capable of catalyzing the conversion of lithium polysulfide is Pt 3 A Ni/C composite material; the lithium polysulfide cathode electrolyte is formed by dissolving lithium polysulfide in lithium sulfur electrolyte, and the concentration of the lithium polysulfide is 1mol/L; the lithium metal negative electrode region comprises a lithium metal negative electrode and lithium sulfur electrolyte, the lithium metal negative electrode is lithium metal, and the diaphragm is a three-layer porous diaphragm (PP/PE/PP); the solvent of the lithium-sulfur electrolyte of the embodiment is represented by the formula R (CH) 2 CH 2 O) n-R 'wherein n =1,R and R' are both methyl, the solute is lithium difluorooxalato borate, and the concentration of the lithium sulfur electrolyte is 1mol/L.
The preparation process of the lithium-sulfur semi-flow battery of the embodiment specifically comprises the following steps:
A、Pt 3 the preparation method of the Ni/C composite material comprises the following specific steps:
(1) Adding a C conductive carrier CNT with the weight of 200mg into a round-bottom flask containing 20mLDMF, and carrying out ultrasonic treatment for 5 hours to obtain carbon-based carrier dispersion liquid with the concentration of 10 mg/mL;
(2) Mixing platinum diacetone (Pt (acac) 2 ) Nickel diacetone (Ni (acac) 2 ) Push button Pt (acac) 2 :Ni(acac) 2 Adding C into the carbon-based carrier dispersion liquid in the step (1) according to a mass ratio of 24;
(3) Heating the mixed dispersion liquid in the step (2) in a constant-temperature water bath at 160 ℃, and reacting for 22 hours;
(4) Centrifugally separating the product obtained in the step (3) to obtain Pt 3 A Ni/C composite material;
B. the preparation method of the working electrode comprises the following specific steps:
(1) 80 parts by weight of active material Pt which is prepared in the step A and can catalyze the conversion of lithium polysulfide 3 Mixing the Ni/C composite material and 10 parts by weight of conductive agent Super p, and grinding to obtain mixed powder;
(2) Stirring and mixing the mixed powder obtained in the step (1) and 10 parts by weight of a binder polyvinylidene fluoride (PVDF), and coating the mixed slurry on a current collector; coating the slurry to the thickness of a current collector of 500 micrometers, and performing vacuum drying at 60 ℃ for 24 hours to remove the solvent to obtain a working electrode;
C. and C, preparing the lithium-sulfur semi-flow battery, namely using the working positive electrode obtained in the step B and the lithium polysulfide catholyte together as a liquid sulfur positive electrode area, using the lithium metal negative electrode and the lithium sulfur electrolyte as a lithium metal negative electrode area, assembling the lithium metal negative electrode and the lithium sulfur electrolyte together with a diaphragm into the battery according to the assembly mode of the commercial liquid flow battery, and stacking the working electrode, the catholyte, the three-layer porous diaphragm (PP/PE/PP), the lithium sulfur electrolyte and the lithium metal negative electrode in sequence in a glove box in an argon atmosphere to obtain the lithium-sulfur semi-flow battery.
The performance of the battery is tested in a battery test system, the charge-discharge cut-off voltage is 1.8V to 2.6V, and the charge-discharge current density is 0.50mA/cm.
Example 9
A lithium-sulfur semi-flow battery with high energy density, high power density and long service life comprises a sulfur flow positive electrode area, a lithium metal negative electrode area and a diaphragm; the positive liquid sulfur area comprises a working electrode and lithium polysulfide catholyte; the working electrode comprises an active material capable of catalyzing the conversion of lithium polysulfide, a conductive agent, a binder and a current collector; the mass ratio of the active material capable of catalyzing the conversion of lithium polysulfide, the conductive agent and the binder is 8; the conductive agent and the binder are common products of commercial batteries, super p is preferably used as the conductive agent, and polyvinylidene fluoride (PVDF) is preferably used as the binder(ii) a The current collector is a stainless steel mesh; the active material capable of catalyzing the conversion of lithium polysulfide is Pt 3 A Ni/C composite material; the lithium polysulfide cathode electrolyte is formed by dissolving lithium polysulfide into lithium sulfur electrolyte, and the concentration of the lithium polysulfide is 1mol/L; the lithium metal negative electrode region comprises a lithium metal negative electrode and lithium sulfur electrolyte, the lithium metal negative electrode is lithium metal, and the diaphragm is a three-layer porous diaphragm (PP/PE/PP); the solvent of the lithium-sulfur electrolyte of the embodiment is R (CH) 2 CH 2 O) n-R 'wherein n =2,R and R' are both ethyl, the solute is lithium difluorophosphate, and the concentration of the lithium sulfur electrolyte is 1mol/L.
The preparation process of the lithium-sulfur semi-flow battery of the embodiment comprises the following specific steps:
A、Pt 3 the preparation method of the Ni/C composite material comprises the following specific steps:
(1) Adding carbon black of a C conductive carrier with the weight of 40mg into a round-bottom flask containing 20mL of DMF, and carrying out ultrasonic treatment for 2 hours to obtain carbon-based carrier dispersion liquid with the concentration of 2 mg/mL;
(2) Mixing platinum diacetone (Pt (acac) 2 ) Nickel diacetone (Ni (acac) 2 ) Push button Pt (acac) 2 :Ni(acac) 2 Adding C into the carbon-based carrier dispersion liquid in the step (1) according to the mass ratio of 16;
(3) Heating the mixed dispersion liquid in the step (2) in a constant-temperature water bath at 170 ℃, and reacting for 20 hours;
(4) Centrifugally separating the product obtained in the step (3) to obtain Pt 3 A Ni/C composite material;
B. the preparation method of the working electrode comprises the following specific steps:
(1) 80 parts by weight of active material Pt which is prepared in the step A and can catalyze the conversion of lithium polysulfide 3 Mixing the Ni/C composite material and 10 parts by weight of conductive agent Super p, and grinding to obtain mixed powder;
(2) Stirring and mixing the mixed powder obtained in the step (1) and 10 parts by weight of a binder polyvinylidene fluoride (PVDF), and coating the mixed slurry on a current collector; coating the slurry to the thickness of a current collector of 50 microns, and performing vacuum drying at 60 ℃ for 24 hours to remove the solvent to obtain a working electrode;
C. and C, preparing the lithium-sulfur semi-flow battery, namely using the working anode obtained in the step B and the lithium polysulfide catholyte together as a liquid sulfur anode region, using the lithium metal cathode and the lithium sulfur electrolyte as a lithium metal cathode region, assembling the lithium metal cathode and the lithium sulfur electrolyte together with a diaphragm into the battery according to the assembly mode of the commercial liquid flow battery, and stacking the working electrode, the catholyte, the three-layer porous diaphragm (PP/PE/PP), the conventional lithium sulfur electrolyte and the lithium metal cathode in sequence in a glove box in an argon atmosphere to obtain the lithium-sulfur semi-flow battery.
The performance of the battery is tested in a battery test system, the charge-discharge cut-off voltage is 1.8V to 2.6V, and the charge-discharge current density is 0.50mA/cm.
FIG. 2 shows Pt in example 9 3 SEM image of Ni/C composite material, and several nm-sized Pt can be seen from FIG. 1 3 Ni is uniformly loaded on the carbon black, which is beneficial to increasing the conductivity of the composite material and increasing the contact area with lithium polysulfide, thereby enhancing the accelerating capacity of the composite material on the conversion of the lithium polysulfide.
FIG. 3 shows Pt in example 9 3 The charge-discharge curve of the lithium-sulfur semi-flow battery using the Ni/C composite material as the working electrode can be seen from the graph, and the charge-discharge curve shows the same charge-discharge platform as the lithium-sulfur battery.
FIG. 4 shows Pt in example 9 3 The cycle performance of the lithium-sulfur semi-flow battery using the Ni/C composite material as the working electrode can be seen, and Pt 3 The lithium-sulfur semi-flow battery with the Ni/C composite material as the working electrode has higher specific capacity, is kept about 550mAh/g, and is stable in circulation, because the Pt is used as the material 3 The Ni/C composite material has excellent and stable catalytic activity for the conversion of lithium polysulfide.

Claims (5)

1. The lithium-sulfur semi-flow battery is characterized by comprising a sulfur flow positive electrode area, a lithium metal negative electrode area and a diaphragm;
the liquid sulfur positive region comprises a working electrode and lithium polysulfide catholyte;
the working electrode comprises an active material, a conductive agent, a binder and a current collector; the mass ratio of the active material to the conductive agent to the binder is 8;
the active material is Ni/C composite material, pt/C composite material or Pt 3 A Ni/C composite material; the current collector is aluminum foil, stainless steel mesh or carbon paper;
the preparation method of the Ni/C composite material comprises the following specific steps:
(1) Ultrasonically treating the C conductive carrier and deionized water for 1~5 hours to obtain a carbon-based carrier dispersion liquid with the concentration of 1-10mg/mL; the C conductive carrier is one of graphene, carbon black and CNT;
(2) Adding nickel acetate or nickel nitrate into the carbon-based carrier dispersion liquid in the step (1) according to the mass ratio of C to Ni of 5-15, and performing ultrasonic treatment for 1~5 hours to obtain a mixed dispersion liquid;
(3) Freezing the mixed dispersion liquid obtained in the step (2) by using liquid nitrogen, and carrying out freeze drying to obtain mixed powder;
(4) Heating the mixed powder in the step (3) to 700-900 ℃ at a heating speed of 5 ℃/min under the protection of Ar gas, calcining for 1~3 hours, and naturally cooling to obtain a Ni/C composite material;
the lithium polysulfide cathode electrolyte is obtained by dissolving lithium polysulfide in lithium sulfur electrolyte;
the lithium metal negative electrode region comprises a lithium metal negative electrode and a lithium sulfur electrolyte; the lithium metal cathode of the lithium metal cathode region is lithium metal or lithium metal alloy;
the solvent of the lithium-sulfur electrolyte is R (CH) 2 CH 2 O) n-R 'wherein n =1-6,R and R' is methyl or ethyl, the solute is lithium difluorooxalato borate, lithium bistrifluoromethylsulfonimide, lithium difluorosulfonimide, lithium difluorophosphate or lithium hexafluorophosphate, and the concentration of the lithium sulfur electrolyte is 1mol/L.
2. The lithium-sulfur semi-flow battery of claim 1, wherein the concentration of lithium polysulfide in the lithium polysulfide catholyte is between 0.1mol/L and 2mol/L.
3. The lithium-sulfur semi-flow battery according to claim 1, wherein the lithium metal alloy is a lithium tin alloy, a lithium silicon alloy, or a lithium copper alloy.
4. The lithium-sulfur semi-flow battery according to claim 1, wherein the preparation method of the Pt/C composite material is the same as that of the Ni/C composite material, and the nickel acetate or nickel nitrate in the step (2) is replaced by platinum acetate or platinum nitrate.
5. The lithium-sulfur semi-flow battery of claim 1, wherein Pt 3 The preparation method of the Ni/C composite material comprises the following specific steps:
(1) Adding a C conductive carrier into DMF, and performing ultrasonic treatment on 8978 zxft For 8978 hours to obtain a carbon-based carrier dispersion liquid with the concentration of 1-10mg/mL; the C conductive carrier is one of graphene, carbon black and CNT;
(2) Adding platinum diacetylacetonate and nickel diacetylacetonate into the carbon-based carrier dispersion liquid in the step (1) according to the mass ratio of the platinum diacetylacetonate to the nickel diacetylacetonate to C of 8;
(3) Heating the mixed dispersion liquid in the step (2) in a constant-temperature water bath at 150-170 ℃, and reacting for 20-24 hours;
(4) Centrifugally separating the product obtained in the step (3), and drying to obtain Pt 3 A Ni/C composite material.
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