CN114122386B - Tin phosphide@carbon composite anode active precursor material, anode active material and anode of lithium sulfur battery and preparation of anode - Google Patents

Tin phosphide@carbon composite anode active precursor material, anode active material and anode of lithium sulfur battery and preparation of anode Download PDF

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CN114122386B
CN114122386B CN202010893569.0A CN202010893569A CN114122386B CN 114122386 B CN114122386 B CN 114122386B CN 202010893569 A CN202010893569 A CN 202010893569A CN 114122386 B CN114122386 B CN 114122386B
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lithium
carbon
sulfur battery
precursor material
simple substance
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CN114122386A (en
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洪波
赖延清
赖俊全
姜怀
张治安
张凯
方静
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Central South University
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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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5805—Phosphides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/08—Other phosphides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/158—Carbon nanotubes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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

Abstract

The invention belongs to the field of lithium metal battery cathode materials. The invention particularly discloses a tin phosphide@carbon composite anode active precursor material of a lithium sulfur battery, which comprises a carbon simple substance skeleton and tin phosphide nano particles embedded on the outer surface of the carbon simple substance skeleton and distributed in a punctiform manner. The invention also discloses the application of the lithium-philic anode active material in the preparation of lithium metal composite electrodes. According to the material disclosed by the invention, the tin phosphide nano points are uniformly and dispersedly distributed on the outer surface of the carbon simple substance skeleton, and based on the innovative morphology and structural characteristics, the abundant specific surface and good conductivity of the carbon simple substance skeleton are combined, so that the local current density is effectively reduced, uniform deposition and dissolution of lithium metal in the continuous circulation process are realized, the growth of dendrites is effectively avoided, and the cycle life of the dendrite in a lithium-sulfur battery is greatly prolonged.

Description

Tin phosphide@carbon composite anode active precursor material, anode active material and anode of lithium sulfur battery and preparation of anode
Technical Field
The invention belongs to the technical field of lithium metal batteries, and particularly relates to the field of lithium metal lithium composite active materials of lithium-sulfur batteries.
Background
The lithium-sulfur battery is a new generation energy storage system with high theoretical energy density and quick charging property, which is constructed by an elemental sulfur anode and a lithium metal cathode. Lithium metal has extremely high theoretical specific capacity 3860mAh g -1 And the lowest electrochemical potential-3.04V (relative to a standard hydrogen electrode), have been considered the most desirable negative electrode material for lithium batteries. However, lithium metal without host structure is liable to generate a huge volume effect during repeated deposition/dissolution, resulting in a greatly reduced cycle life; on the other hand, the inherent unevenness of the surface of the lithium metal causes uneven lithium deposition, and then uncontrollable lithium dendrites are initiated, so that the battery is short-circuited or even exploded, and further industrial application of the lithium metal cathode is hindered.
At present, the volume effect in the lithium metal circulation process is mainly eliminated by constructing a 3D porous framework structure, which comprises graphene, hollow carbon spheres, carbon fibers, glass fibers, foam metal frameworks and the like, wherein the carbon materials are important host materials for inhibiting the volume change of lithium metal due to the advantages of light weight, good conductivity, strong toughness and the like, for example, the commercial carbon nanofibers are subjected to mixed acid treatment and suction filtration to obtain carbon nanofiber films, and the carbon nanofibers can form ideal conductive networks to ensure rapid electronic conduction; compared with pure lithium metal, the high specific surface area can effectively reduce the local current density; however, at high current densities, lithium metal deposition is not uniform, resulting in uncontrolled lithium dendrites, reduced coulombic efficiency, and reduced cycle life.
Aiming at the problem of uneven deposition of lithium metal in a three-dimensional space, researchers mainly modify the surface of a carbon skeleton at present. Lai Yanqing et al [ Hong B, fan H, cheng X B, et al, spatially uniform deposition of lithium metal in D Janus hosts [ J ]].Energy Storage Materials,2019,16: 259-266.]And the metal spraying treatment is carried out on the lower surface of the carbon paper, so that lithium is guided to be uniformly deposited in the three-dimensional structure, and the coulomb efficiency and the cycle stability are effectively improved. Hu Liangbing et al [ Zhang Y, liu B, hitz E, et al A carbon-based 3D current collector with surface protection for Li metal anode[J ]].Nano Research,2017,10:1356-1365.]Surface modification is carried out on the carbon nano tube by chemical vapor deposition to prepare Al 2 O 3 The layer-modified carbon nanotube sponge has high specific surface area and stable Al 2 O 3 The performance of the lithium anode is greatly improved at the layer interface.
Although the current research has made great progress, there is still a need for further research to maintain uniform deposition of lithium, lower volume effect, and reduce internal polarization of lithium negative electrode at high current density.
The invention comprises the following steps:
aiming at the problems of nonuniform deposition and uncontrollable growth of lithium dendrite in the circulating process of the existing lithium-sulfur battery metal lithium anode material, the invention provides a tin phosphide@carbon composite anode active precursor material (precursor material for short) of a lithium-sulfur battery, and aims to provide a method capable of inducing uniform nucleation and deposition of lithium, improving the problem of nonuniform deposition of lithium under high current, reducing volume effect, reducing internal polarization of a lithium anode and improving the circulating performance of the lithium-sulfur battery metal lithium anode.
The second object of the invention is to provide a method for preparing the precursor material.
A third object of the present invention is to provide a use of the precursor material.
A fourth object of the present invention is to provide a lithium metal-sulfur battery lithium metal composite anode active material (also referred to as a lithium metal composite active material or simply referred to as an active material in the present invention).
The fifth object of the present invention is to provide a method for preparing the composite anode active material by using the precursor material.
The sixth object of the present invention is to provide a negative electrode for a lithium-sulfur battery. Aims to obtain a dendrite-free lithium anode (3-8mA.cm) -2 ) Has good cycle performance.
The seventh object of the invention is to provide a method for preparing the negative electrode of the lithium-sulfur battery based on the precursor material.
An eighth object of the present invention is to provide a lithium-sulfur battery equipped with the negative electrode.
A lithium sulfur battery tin phosphide@carbon composite anode active precursor material comprises a carbon simple substance skeleton and tin phosphide nano particles which are inlaid on the outer surface of the carbon simple substance skeleton and are distributed in a punctiform manner (uniformly dispersed);
the carbon simple substance skeleton is one-dimensional carbon simple substance and/or zero-dimensional carbon simple substance.
The invention belongs to the technical field of lithium metal anode materials of lithium sulfur batteries, and aims to solve the problems that the lithium metal anode of the lithium sulfur battery is puzzled with uneven deposition, has larger volume effect and has non-ideal electrochemical performance. In order to solve the technical problem, the invention researches and discovers that the one-dimensional carbon simple substance and/or the zero-dimensional carbon simple substance are innovatively adopted as a substrate, and tin phosphide nano points are uniformly and dispersedly distributed on the outer surface of the substrate, so that the deposition uniformity and the structural stability of a lithium metal anode of the lithium sulfur battery in the circulation process can be effectively improved based on the innovative morphology and the structural characteristics, and the electrochemical performance of the lithium sulfur battery, particularly the circulation stability under large current can be unexpectedly improved.
In the invention, the precursor material has the structural characteristics of the one-dimensional carbon simple substance and/or the zero-dimensional carbon simple substance substrate and the dispersion distribution characteristics of the tin phosphide nano particles on the outer surface of the substrate, which are key to realizing good capacity, coulomb efficiency and cycle stability of the precursor material in a lithium sulfur battery.
The carbon simple substance skeleton is at least one of a carbon nano tube, a carbon nano fiber, a carbon hollow sphere and a carbon solid sphere; the carbon simple substance skeleton is graphitized carbon and/or amorphous carbon.
Preferably, the carbon simple substance skeleton is a carbon nano tube.
Further preferably, the diameter of the carbon nanotube is 5-100nm; further preferably 10-40nm;
preferably, the thickness of the tube wall of the carbon nano tube is 1-20nm; further preferably 4-8nm.
In the invention, the dispersion distribution mode of the tin phosphide particles and the distribution mode of the outer surface of the substrate are key to realizing good electrochemical performance in a lithium sulfur battery. It is found that for lithium sulfur battery metal lithium composite cathodes, tin phosphide particles distributed uniformly and in a dot shape can effectively reduce nucleation overpotential of lithium deposition and improve uniform deposition of metal lithium. Further research shows that the control of the particle size and the distribution amount of the tin phosphide particles is beneficial to further improving the long-acting cycle stability of the lithium metal battery of the lithium sulfur battery.
Preferably, the particle size of the tin phosphide particles is 0.1-10nm; further preferably 3-6nm;
preferably, in the precursor material, the content of the tin phosphide particles is 5-50 wt%; more preferably 10 to 30wt%.
The invention also provides a preparation method of the lithium sulfur battery tin phosphide@carbon composite anode active precursor material, which comprises the steps of carrying out solvothermal reaction on a raw material solution containing a Sn (II) source, a carbon simple substance skeleton and alcohol, and forming Sn oxides distributed in a punctiform manner on the surface of the carbon simple substance skeleton; then carrying out solid-phase phosphating treatment with a phosphorus source in an inert atmosphere to obtain the catalyst;
in the raw material solution, the molar concentration of the Sn (II) source (calculated by Sn (II) ions) is 0.2-1 mol/L;
the concentration of the carbon simple substance skeleton is 15-40 g/L.
According to the research of the invention, the one-dimensional and zero-dimensional carbon simple substance is innovatively adopted as a substrate, and the combination control of the concentration of the Sn (II) source and the carbon simple substance skeleton in the solvent of the bivalent Sn (II) source, the solvent of the solvothermal reaction starting solution is matched, so that the formation of the dot-shaped Sn oxide on the surface of the carbon simple substance skeleton in different positions is facilitated, and the solid-phase phosphating treatment is further matched, so that the dot-shaped Sn oxide can be converted into Sn phosphide in situ, and the precursor material with the morphology is obtained.
In the preparation method, how to successfully construct the dot-shaped Sn oxide in the solvothermal process is a key for ensuring that the prepared material has good effect in the aspect of being used as a metal lithium composite negative electrode of a lithium-sulfur battery. For this reason, the invention has been innovatively studied and found that the Sn oxide material of the punctiform distribution morphology can be surprisingly and successfully constructed by providing an ectopic deposition outer surface with one-dimensional, zero-dimensional carbon elements and based on a combined control of the solvothermal process system, sn (II) source and carbon element concentration. On the basis of the Sn oxide material, the Sn oxide material is further matched with solid-phase phosphating treatment, so that the Sn oxide can be converted into phosphide in situ, and the punctiform distribution form is successfully reserved.
Preferably, the Sn (II) source is at least one of stannous chloride and stannous sulfate.
Preferably, the alcohol is at least one of ethanol, methanol and 2-propanol.
In the invention, controlling the molar concentration of the Sn (II) source helps to successfully construct the punctiform distribution material with good influence effect in the lithium-sulfur battery. The concentration is not controlled in the required range, and the materials with the dot distribution are difficult to obtain, which is not beneficial to the electrochemical promotion of the lithium-sulfur battery.
Preferably, the molar concentration of the Sn (II) source in the raw material solution is 0.6 to 0.8mol/L.
Similarly, on the basis of controlling the molar concentration of the Sn (II) source, the concentration of the carbon simple substance skeleton is further controlled in a synergistic way, so that the precursor material with good application effect in the lithium-sulfur battery can be further obtained.
Preferably, in the raw material solution, the molar concentration of the carbon element skeleton is 20-40 g/L.
The research of the invention also finds that under the solvothermal system, the distribution form and structure of Sn in the carbon simple substance substrate can be further controlled by further matching with the temperature control of solvothermal. Preferably, the temperature of the solvothermal is 100-250 ℃, preferably 140-190 ℃; still more preferably 150 to 160 ℃. It is found that under the preferable solvothermal system and solvothermal temperature, the punctiform distribution form of the Sn oxide can be effectively controlled, and the performance of the Sn oxide serving as a lithium metal anode precursor material of a lithium-sulfur battery can be further improved.
Preferably, the solvothermal time is 5-15 hours, preferably 8-12 hours;
according to the invention, on the basis of the solvothermal method, the solid-phase phosphating means is further matched, so that the coordination can be realized, the Sn oxides in dot distribution are converted into phosphide in an original state, and the dot distribution state is maintained and improved, thereby being beneficial to the coordination improvement of the performance of the Sn oxides in the cathode of the lithium-sulfur battery.
Preferably, the phosphorus source is at least one of metaphosphate and hypophosphite.
Preferably, the amount of the phosphorus source is not less than the theoretical molar amount by which Sn is completely reacted, preferably 1 to 4 times the theoretical molar amount.
Preferably, the mass ratio of the phosphorus source to the stannic oxide@carbon composite active precursor material is 1:1 to 6: 1.
The solid-phase phosphating treatment is carried out by embedding SnO on the surface in a punctiform manner 2 Mixing the carbon composite material of the particles with a phosphorus source material, heating in an inert atmosphere, and reacting the phosphorus source material to generate PH 3 By means of pH 3 SnO is prepared 2 Particle reduction to Sn 4 P 3 Particles, and keep the original SnO 2 The structure and dot-like distribution characteristics of the particles, and the precursor material is obtained.
Preferably, the temperature of the solid-phase phosphating treatment is 250 to 500 ℃, more preferably 250 to 300 ℃.
Preferably, the temperature rising rate of the solid-phase phosphating process is 1 ℃/min to 2 ℃/min, more preferably 1 ℃ to 1.5 ℃/min.
Preferably, the solid-phase phosphating is carried out for a period of time of 10min to 3 hours, preferably 10min to 1 hour.
The invention also discloses application of the tin phosphide@carbon composite anode active precursor material of the lithium sulfur battery, and the lithium-carrying treatment (lithiation-induced lithium carrying) is carried out on the precursor material to prepare the metal lithium composite anode active material of the lithium sulfur battery.
The application can adopt the existing method to fill lithium into the precursor material, so that the precursor material reacts with lithium and carries out induced lithium loading, and the lithium-sulfur battery metal lithium composite anode material is obtained.
The invention also provides a lithium metal composite anode active material (also called as a lithium metal composite active material) of the lithium sulfur battery, which comprises the carbon simple substance skeleton, an induction layer compounded on the outer surface of the carbon simple substance skeleton and a lithium metal simple substance compounded on the surface of the induction layer; the induction layer comprises Li-Sn alloy and Li 3 P。
The metal lithium composite active material of the invention uniformly distributes Sn in a punctiform manner at the initial stage of the lithiation process 4 P 3 The particles react with lithium to form a lithium-containing material comprising Li 3 And the induction layer of the P and Sn-Li alloy can effectively reduce the lithium nucleation overpotential, so that the lithium metal is uniformly deposited on the induction layer, and a compact lithium simple substance deposition layer is obtained.
The metal lithium composite negative electrode active material of the lithium sulfur battery is obtained by carrying lithium after lithiation of the tin phosphide@carbon composite negative electrode active precursor material of the lithium sulfur battery.
The invention also provides a lithium-sulfur battery anode, which comprises the lithium-sulfur battery metal lithium composite anode active material.
Preferably, the lithium sulfur battery cathode comprises a cathode current collector and a metal lithium active layer compounded on the surface of the current collector; the metal lithium active layer comprises conductive carbon, the lithium metal lithium composite anode active material of the lithium-sulfur battery and a binder for binding and compositing the material on the surface of a current collector.
Preferably, the metallic lithium is composited on the surface of the induction layer and is also filled in gaps among the metallic lithium composite anode active material particles of the lithium-sulfur battery.
The invention also provides a preparation method of the lithium-sulfur battery cathode, which comprises slurrying the precursor material, the conductive agent and the binder, compounding the slurried precursor material, the conductive agent and the binder on the surface of a cathode current collector, solidifying and drying the slurried precursor material and the conductive agent to obtain a cathode precursor; and then carrying out lithium loading (filling lithium) treatment on the anode precursor, carrying out pre-lithiation on the precursor material, and inducing deposition of lithium metal on the surface of the lithiation inducing layer and in gaps of the precursor material to prepare the anode of the lithium-sulfur battery.
In the invention, the precursor material can be subjected to spray treatment to obtain secondary particles of the precursor material, and then slurried with the conductive agent and the binder for coating and carrying lithium to obtain the negative electrode.
In the invention, the lithium loading treatment method is melt lithium filling or electrodeposition lithium filling; more preferably, lithium is filled by electrodeposition.
The current collector may be a current collector known in the industry, such as a planar metal current collector, copper foil, or the like.
The binder may be an adhesive polymer such as PVDF, which is well known in the industry.
The lithium carrying amount in the negative electrode of the lithium-sulfur battery can be adjusted according to the requirement, and the preferable lithium carrying amount is 1-20 mA/cm 2 。
The invention also provides an application of the lithium-sulfur battery cathode, which is used as the cathode of the lithium-sulfur battery.
The invention also provides a lithium sulfur battery, which comprises the negative electrode.
The beneficial effects are that:
1. the invention provides a tin phosphide@carbon composite anode active precursor material for a lithium sulfur battery, and the material with the morphology is found to have unexpected technical effects on the aspect of a lithium metal anode of the lithium sulfur battery.
The precursor material takes a one-dimensional and zero-dimensional carbon simple substance as a substrate, and tin phosphide is uniformly and dispersedly distributed on the surface of the precursor material, and researches show that the precursor material has a stable structure and good lithium affinity, can effectively reduce lithium nucleation overpotential, realizes uniform deposition of lithium metal, and can bring excellent technical effects when being applied to the preparation of lithium metal negative electrodes of lithium-sulfur batteries. In addition, the precursor material can greatly increase the specific surface area and reduce the apparent current density; the abundant and uniformly distributed tin phosphide particles provide lithium-philic sites which can preferentially induce lithium metal nucleation, so that uniform deposition of lithium metal in the porous carbon skeleton cavity is realized, and the volume effect is slowed down.
2. The precursor material is directly loaded with lithium, or coated with lithium, or sprayed into secondary particles and then coated with lithium, so that the lithium-sulfur battery composite metal lithium anode can be obtained.
Furthermore, the composite lithium metal anode made of the precursor material can realize high coulombic efficiency, long cycle life and high energy density under high current density. In addition, the one-dimensional and zero-dimensional carbon skeleton has excellent conductivity, and meanwhile, the lithium deposition non-uniformity under high current density can be well relieved by rich specific surface energy, so that good electrochemical conditions are created for realizing stable deposition/dissolution of lithium metal.
3. In order to obtain the composite material with the morphological characteristics and the composite anode, the invention also provides a preparation process of phosphating under the solvothermal-inert atmosphere of the carbon skeleton and Sn (II), and innovatively discovers that the solid-phase phosphating means can be further matched by cooperatively controlling parameters such as a solvothermal system, the concentration of Sn (II) and a carbon substrate in solvothermal, the temperature of solvothermal and the like, so that the material with the special morphology and excellent electrochemical performance in a lithium metal battery is obtained.
Detailed Description
The following is a detailed description of preferred embodiments of the invention and is not intended to limit the invention to the embodiments described, but rather to limit the invention to those embodiments and variations and alternative compounds that are common in the art are intended to be included within the scope of the invention as defined in the claims.
In the following cases, the heating rate during heating was 1 to 1.5℃per minute unless specifically stated.
Example 1
The outer diameter of the Carbon Nano Tube (CNT) is 40nm, and the tube wall thickness is 7nm. First 4.51g SnCl 2 ·2H 2 O (0.02 moL) was dissolved in 25mL of ethanol (0.8 moL/L), and 1.00g of carbon nanotubes was added to completely immerse them in the solution. After magnetic stirring for 60 minutes, the resulting suspension was transferred to an autoclave, heated to 150 ℃ and solvothermal reacted for 10 hours. Then washing the obtained product with deionized water and drying to obtain SnO 2 @cnt composite material. SnO is prepared 2 Mixing the @ CNT composite material (1.4 g) with 6g of sodium hypophosphite, uniformly mixing, placing into a tube furnace, introducing argon, heating to 280 ℃, preserving heat for 30min, naturally cooling, washing with deionized water, and drying to obtain Sn 4 P 3 @cnt composite material.
Sn is mixed with 4 P 3 @cnt composite negative electrode precursor material (prepared Sn 4 P 3 @cnt composite) was mixed with binder PVDF and acetylene black in a mass ratio of 8:1:1, slurried with NMP and then uniformly coated on copper foil, dried to serve as a working electrode, and a metallic lithium sheet as a counter electrode, with 1M LiTFSI/dol:dme (volume ratio=1:1) containing 1wt.% LiNO 3 The electrolyte was subjected to button cell (half cell) assembly, lithium deposition test and charge-discharge cycle test. Meanwhile, the carbon nanotube electrode is used as a reference sample for carrying out corresponding deposition test and charge-discharge cycle test.
Experimental results show that, relative to pure carbon nanotubes with smooth surfaces, granular Sn 4 P 3 The particles are uniformly and dispersedly compounded on the outer surface of the carbon nano tube, sn 4 P 3 The average particle diameter of the particles is about 5nm, sn 4 P 3 The content was 30wt.%. In subsequent lithium deposition experiments, metallic lithium was uniformly nucleated and deposited on Sn 4 P 3 The surface of the @ CNT composite avoids uneven lithium deposition and the occurrence of lithium dendrites.
At 3mA/cm 2 At current density, sn 4 P 3 The cycle life of the composite electrode made of the CNT material under the same coulombic efficiency is more than 3 times of that of a pure carbon nanotube (carbon nanotube before the composite).
Example 2
The only difference compared to example 1 is that carbon nanofibers are used instead of the carbon nanotubes, specifically:
carbon Nanofibers (CNF) with a diameter of 100nm. First 4.51g SnCl 2 ·2H 2 O (0.02 moL) was dissolved in 25mL of ethanol, and 1.00g of carbon nanofibers were added to completely immerse them in the solution. After magnetic stirring for 60 minutes, the resulting suspension was transferred to an autoclave, heated to 150 ℃ and solvothermal reacted for 10 hours. Then washing the obtained product with deionized water and drying to obtain SnO 2 @ CNF composite. SnO is prepared 2 Mixing @ CNF composite (1.4 g) with 6g sodium hypophosphite, placing in a tube furnace after uniform mixing, introducing argon, heating to 280 ℃, preserving heat for 30min, naturally cooling, washing with deionized water, and drying to obtain Sn 4 P 3 @ CNF composite.
Sn is mixed with 4 P 3 Mixing the @ CNF composite anode precursor material, a binder PVDF and acetylene black in a mass ratio of 8:1:1, adding NMP, pulping, uniformly coating on a copper foil, drying to serve as a working electrode, taking a metal lithium sheet as a counter electrode, and taking 1M LiTFSI/DOL:DME (volume ratio=1:1) to contain 1wt.% LiNO 3 And (3) performing button cell battery assembly, lithium deposition test and charge-discharge cycle test for the electrolyte. Meanwhile, the carbon nanofiber electrode is used as a reference sample to perform corresponding deposition test and charge-discharge cycle testAnd (5) testing.
As a result of experiments, it was found that Sn in the form of particles was compared with pure carbon nanofibers 4 P 3 The particles are uniformly dispersed and distributed on the surface of the carbon nanofiber in a punctiform manner, and Sn 4 P 3 The average particle diameter of the particles is about 5nm, sn 4 P 3 The content was 20wt.%. In subsequent lithium deposition experiments, metallic lithium was uniformly nucleated and deposited on Sn 4 P 3 The surface of the @ CNF composite and the gaps formed by the surface of the @ CNF composite avoid uneven lithium deposition and occurrence of lithium dendrites.
At 3mA/cm 2 At current density, sn 4 P 3 The cycle life of the composite electrode made of the @ CNF material under the same coulombic efficiency is more than 2 times that of pure carbon nanofiber (CNF before treatment).
Example 3
The difference from example 1 is mainly that the Sn concentration is 1M, specifically:
the outer diameter of the Carbon Nano Tube (CNT) is 40nm, and the tube wall thickness is 7nm. First, 5.64g of SnCl 2 ·2H 2 O (0.025 moL) was dissolved in 25mL of ethanol (1 moL/L), and 1.00g of carbon nanotubes was added to completely immerse them in the solution. After magnetic stirring for 60 minutes, the resulting suspension was transferred to an autoclave, heated to 150 ℃ and solvothermal reacted for 10 hours. Then washing the obtained product with deionized water and drying to obtain SnO 2 @cnt composite material. SnO is prepared 2 Mixing 1.4g of the@CNT composite material with 6g of sodium hypophosphite, uniformly mixing, placing into a tube furnace, introducing argon, heating to 280 ℃, preserving heat for 30min, naturally cooling, washing with deionized water, and drying to obtain Sn 4 P 3 @cnt composite material.
SnCl 2 ·2H 2 When the concentration of the O ethanol solution is 1mol/L, sn on the surface of the carbon nano tube 4 P 3 The particles are unevenly distributed and partially stacked and agglomerated.
Example 3-1
The difference compared to example 3 is that the concentration of Sn in the solvothermal starting solution is 0.2M, producing Sn 4 P 3 The active precursor material of the anode of the CNT composite.
Example 3-2
The difference compared to example 3 is that the concentration of Sn in the solvothermal starting solution is 0.5M, producing Sn 4 P 3 The active precursor material of the anode of the CNT composite.
Examples 3 to 3
The difference compared to example 3 is that the concentration of Sn in the solvothermal starting solution is 0.6M, producing Sn 4 P 3 The active precursor material of the anode of the CNT composite.
As can be seen from examples 1, 3-1, 3-2 and 3-3, 0.2mol/L SnCl 2 ·2H 2 The obvious Sn is difficult to see on the surface of the carbon nano tube treated by the O ethanol solution 4 P 3 Particle, snCl 2 ·2H 2 After the molar concentration of O reaches 0.5mol/L, sn 4 P 3 The particles are fewer and are unevenly distributed, and a large blank exists on part of the surface. Sn is uniformly embedded on the surface of the carbon nano tube at the mol/L of 0.5-0.8 4 P 3 Nanoparticle, and Sn 4 P 3 The particle size of the nano particles is about 5 nm. While SnCl 2 ·2H 2 After the molar concentration of O is increased to 1mol/L, sn 4 P 3 Uneven particle distribution and increased particle size, sn 4 P 3 The particle portions are stacked and agglomerated. Thus, snCl 2 ·2H 2 The concentration of O in the ethanol solution is preferably 0.6 to 0.8mol/L.
Half cells were assembled and electrochemical measurements were performed as in example 1:
sn prepared in examples 1, 3-1 and 3-2 4 P 3 Mixing the@CNT composite material with a binder PVDF and acetylene black according to the mass ratio of 8:1:1, adding NMP, slurrying, uniformly coating on a copper foil, drying to serve as a working electrode, taking a metal lithium sheet as a counter electrode, and taking 1M LiTFSI/DOL:DME (volume ratio=1:1) to contain 1wt.% LiNO 3 And (3) performing button cell battery assembly, lithium deposition test and charge-discharge cycle test for the electrolyte. At 3mA/cm 2 The current density of (2) was selected for charge-discharge cycle testing, and the test results are shown in table 1 below:
TABLE 1
The result shows that the tin phosphide@carbon composite anode active material obtained when the concentration of the Sn (II) source in the solvothermal reaction is 0.8M has the optimal electrode electrochemical performance.
Example 4
The difference compared with example 1 is mainly that Sn is produced at a solvothermal temperature of 120 DEG C 4 P 3 The active precursor material of the anode of the CNT composite.
Example 4-1
The difference compared with example 4 is that Sn is produced at a solvothermal temperature of 140 DEG C 4 P 3 The active precursor material of the anode of the CNT composite.
Example 4-2
The difference compared with example 4 is that Sn is produced at a solvothermal temperature of 160 DEG C 4 P 3 The active precursor material of the anode of the CNT composite.
Examples 4 to 3
The difference compared with example 4 is that Sn is produced at a solvothermal temperature of 180 DEG C 4 P 3 The active precursor material of the anode of the CNT composite.
Examples 4 to 4
The difference compared with example 4 is that Sn is produced at a solvothermal temperature of 200 DEG C 4 P 3 The active precursor material of the anode of the CNT composite.
As is clear from examples 1, 4-1, 4-2, 4-3 and 4-4, the surface Sn of the carbon nanotube is at 120℃solvothermal temperature 4 P 3 Less particles; when the temperature is raised to 140 ℃, 150 ℃, 160 ℃ and 180 ℃, the surface Sn of the carbon nano tube 4 P 3 The particle quantity is improved and distributed uniformly, which is beneficial to forming the characteristic morphology. And Sn formed by the solvent at a solvothermal temperature of 200 DEG C 4 P 3 The particle size of the particles is increased, the number of the particles is reduced, and the Sn is not favored 4 P 3 Uniformity of particlesDistribution. Therefore, the solvothermal reaction temperature is 100-250 ℃, more preferably 140-180 ℃, which is favorable for forming the dot-shaped and uniformly distributed Sn on the surface of the carbon skeleton 4 P 3 And (3) particles.
Electrochemical performance test:
the electrochemical measurements were carried out as in example 1, in particular:
sn prepared in example 1, example 4-1, example 4-2, example 4-3 and example 4-4 thereof 4 P 3 Mixing the@CNT composite material with a binder PVDF and acetylene black according to the mass ratio of 8:1:1, adding NMP, slurrying, uniformly coating on a copper foil, drying to serve as a working electrode, taking a metal lithium sheet as a counter electrode, and taking 1M LiTFSI/DOL:DME (volume ratio=1:1) to contain 1wt.% LiNO 3 And (3) performing button cell battery assembly, lithium deposition test and charge-discharge cycle test for the electrolyte. At 3mA/cm 2 The current density of (2) was selected for charge-discharge cycle testing, and the test results are shown in table 2 below:
TABLE 2
The result shows that when the reaction temperature in the solvothermal reaction is 150-160 ℃, the obtained tin phosphide@carbon composite anode active material has optimal electrode electrochemical performance.
Example 5
The electrical property of the lithium sulfur battery (full battery) is measured, specifically:
sn prepared in example 1 4 P 3 Mixing the @ CNT composite anode precursor material, a binder PVDF and acetylene black according to the mass ratio of 8:1:1, adding NMP, pulping, uniformly coating on a copper foil, drying to serve as a working electrode, taking a metal lithium sheet as a counter electrode, and taking 1M LiTFSI/DOL:DME (volume ratio=1:1) to contain 1wt.% LiNO 3 Is electrolyte, at current density of 0.5mA/cm 2 Lower deposition5mAh/cm 2 And preparing the metal lithium composite anode. Then, the lithium sulfur battery is formed with a mesoporous carbon positive electrode rich in S simple substance, and 1M LiTFSI/DOL: DME (volume ratio=1:1) contains 1wt.% LiNO 3 In the electrolyte of (2), a charge-discharge cycle test was performed at 1C.
Example 6:
the electrical property of the lithium sulfur battery (full battery) is measured, specifically:
the difference from example 5 is that Sn is 4 P 3 The lithium-carrying (lithium filling) treatment method of the CNT composite anode precursor material is melt lithium filling, namely: and (3) contacting the grade sheet containing the anode precursor material with molten metal lithium in an oxygen-free dry environment at 250 ℃ to obtain the metal lithium composite anode. Then, the lithium sulfur battery is formed with a mesoporous carbon positive electrode rich in S simple substance, and 1M LiTFSI/DOL: DME (volume ratio=1:1) contains 1wt.% LiNO 3 In the electrolyte of (2), a charge-discharge cycle test was performed at 1C.
The experimental test-related results are shown in table 3:
TABLE 3 Table 3
The results show that Sn obtained by electrodeposition lithium filling 4 P 3 The electrochemical performance of the@CNT composite lithium metal anode is optimal.

Claims (34)

1. A lithium sulfur battery stannum phosphide@carbon composite anode active precursor material is characterized in that: comprises a carbon simple substance skeleton and tin phosphide nano particles which are inlaid on the outer surface of the carbon simple substance skeleton and distributed in a punctiform manner;
the carbon simple substance skeleton is one-dimensional carbon simple substance and/or zero-dimensional carbon simple substance.
2. The lithium sulfur battery tin phosphide @ carbon composite anode active precursor material as set forth in claim 1, wherein: the carbon simple substance skeleton is at least one of a carbon nano tube, a carbon nano fiber, a carbon hollow sphere and a carbon solid sphere; the carbon simple substance skeleton is graphitized carbon and/or amorphous carbon.
3. The lithium sulfur battery tin phosphide @ carbon composite anode active precursor material as set forth in claim 1, wherein: the carbon simple substance skeleton is a carbon nano tube.
4. The lithium sulfur battery tin phosphide @ carbon composite anode active precursor material as set forth in claim 3, wherein: the diameter of the carbon nano tube is 5-100nm.
5. The lithium sulfur battery tin phosphide @ carbon composite anode active precursor material as defined in claim 4, wherein: the diameter of the carbon nano tube is 10-40nm.
6. The lithium sulfur battery tin phosphide @ carbon composite anode active precursor material as set forth in claim 3, wherein: the thickness of the tube wall of the carbon nano tube is 1-20nm.
7. The lithium sulfur battery tin phosphide @ carbon composite anode active precursor material as defined in claim 6, wherein: the thickness of the tube wall of the carbon nano tube is 4-8nm.
8. The lithium sulfur battery tin phosphide @ carbon composite anode active precursor material as set forth in claim 1, wherein: the grain diameter of the tin phosphide nano-particle is 0.1-10nm.
9. The lithium sulfur battery tin phosphide @ carbon composite anode active precursor material as set forth in claim 8, wherein: the grain diameter of the tin phosphide nano-particle is 3-6nm.
10. The lithium sulfur battery tin phosphide @ carbon composite anode active precursor material as set forth in claim 1, wherein: in the tin phosphide@carbon composite anode active precursor material, the content of tin phosphide nano particles is 5-50 wt%.
11. The lithium sulfur battery tin phosphide @ carbon composite anode active precursor material as set forth in claim 10, wherein: in the tin phosphide@carbon composite anode active precursor material, the content of tin phosphide nano particles is 10-30wt%.
12. A method for preparing the tin phosphide @ carbon composite anode active precursor material of a lithium-sulfur battery according to any one of claims 1-11, which is characterized by comprising the following steps: carrying out solvothermal reaction on a raw material solution containing a Sn (II) source, a carbon simple substance skeleton and alcohol, and forming Sn oxides distributed in a punctiform manner on the surface of the carbon simple substance skeleton; then carrying out solid-phase phosphating treatment with a phosphorus source in an inert atmosphere to obtain the catalyst;
in the raw material solution, the molar concentration of the Sn (II) source is 0.2-1 mol/L;
the concentration of the carbon simple substance skeleton is 15-40 g/L.
13. The method of manufacturing as claimed in claim 12, wherein: the Sn (II) source is at least one of stannous chloride and stannous sulfate.
14. The method of manufacturing as claimed in claim 12, wherein: the alcohol is at least one of ethanol, methanol and 2-propanol.
15. The method of manufacturing as claimed in claim 12, wherein: the concentration of the carbon simple substance skeleton is 20-40 g/L.
16. The method of manufacturing as claimed in claim 12, wherein: the solvothermal temperature is 100-250 ℃.
17. The method of manufacturing as claimed in claim 12, wherein: the solvothermal temperature is 140-190 ℃.
18. The method of manufacturing as claimed in claim 12, wherein: the solvothermal time is 5-15 h.
19. The method of manufacturing as claimed in claim 12, wherein: the solvothermal time is 8-12 h.
20. The method of manufacturing as claimed in claim 12, wherein: the phosphorus source is at least one of metaphosphate and hypophosphite.
21. The method of manufacturing as claimed in claim 12, wherein: the amount of the phosphorus source used is not less than the theoretical molar amount for completely reacting Sn.
22. The method of manufacturing as claimed in claim 21, wherein: the use amount of the phosphorus source is not less than 1-4 times of the theoretical molar amount of the Sn to be completely reacted.
23. The method of manufacturing as claimed in claim 12, wherein: the temperature of the solid-phase phosphating treatment is 250-500 ℃; the temperature rising rate is 1-2 ℃/min.
24. The method of manufacturing as claimed in claim 12, wherein: the solid-phase phosphating treatment time is 10 min-3 h.
25. The method of manufacturing as claimed in claim 24, wherein: the solid-phase phosphating treatment time is 10 min-1 h.
26. The application of the tin phosphide@carbon composite negative electrode active precursor material for a lithium sulfur battery as claimed in any one of claims 1 to 11 or the tin phosphide@carbon composite negative electrode active precursor material for a lithium sulfur battery as prepared by the preparation method as claimed in any one of claims 12 to 25, which is characterized in that: and carrying out lithium loading treatment to obtain the lithium metal lithium composite anode active material of the lithium-sulfur battery.
27. The lithium metal-lithium composite anode active material of the lithium-sulfur battery is characterized by comprising a carbon simple substance skeleton, an induction layer compounded on the outer surface of the carbon simple substance skeleton, and a metal lithium simple substance compounded on the surface of the induction layer; the induction layer comprises Li-Sn alloy and Li 3 P。
28. The lithium metal sulfide battery negative electrode active material according to claim 27, wherein the lithium metal sulfide battery negative electrode active material is obtained by carrying lithium from a tin phosphide@carbon composite negative electrode active precursor material of a lithium sulfur battery according to any one of claims 1 to 11 or a tin phosphide@carbon composite negative electrode active precursor material of a lithium sulfur battery prepared by the preparation method according to any one of claims 12 to 25.
29. A negative electrode for a lithium-sulfur battery, comprising the lithium metal-lithium composite negative electrode active material for a lithium-sulfur battery according to claim 27 or 28.
30. The negative electrode of lithium-sulfur battery of claim 29 comprising a negative electrode current collector, a metallic lithium active layer composited on the surface of the current collector; the metal lithium active layer comprises conductive carbon, the lithium metal lithium composite anode active material of the lithium-sulfur battery and a binder for binding and compositing the material on the surface of a current collector.
31. The lithium-sulfur battery anode according to claim 29 or 30, wherein the metallic lithium is composited on the surface of the inducing layer and is further filled in the gaps between the metallic lithium composite anode active material particles of the lithium-sulfur battery.
32. A preparation method of a lithium-sulfur battery anode, which is characterized in that the precursor material of any one of claims 1-11 or the precursor material prepared by any one of the preparation methods of claims 12-25, a conductive agent and a binder are pulped and compounded on the surface of an anode current collector, and the anode precursor is obtained by solidification and drying; and carrying out lithium carrying treatment on the anode precursor, carrying out pre-lithiation on the precursor material, and inducing deposition of lithium metal on the surface of the lithiation inducing layer and in gaps of the precursor material to prepare the anode of the lithium-sulfur battery.
33. The method for preparing a negative electrode of a lithium-sulfur battery as claimed in claim 32, wherein the lithium-carrying treatment is melt-filling or electro-deposition-filling.
34. A lithium-sulfur battery comprising the negative electrode according to any one of claims 29 to 31 or the negative electrode produced by the production method according to any one of claims 32 to 33.
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