CN111180710A - Nickel-cobalt-manganese multi-metal @ graphitized carbon @ hierarchical porous carbon material, preparation thereof and application thereof in lithium-sulfur battery - Google Patents
Nickel-cobalt-manganese multi-metal @ graphitized carbon @ hierarchical porous carbon material, preparation thereof and application thereof in lithium-sulfur battery Download PDFInfo
- Publication number
- CN111180710A CN111180710A CN202010048893.2A CN202010048893A CN111180710A CN 111180710 A CN111180710 A CN 111180710A CN 202010048893 A CN202010048893 A CN 202010048893A CN 111180710 A CN111180710 A CN 111180710A
- Authority
- CN
- China
- Prior art keywords
- cobalt
- nickel
- manganese
- carbon
- positive electrode
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- 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
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- 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
- C01B32/20—Graphite
- C01B32/205—Preparation
-
- 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
- H01M10/54—Reclaiming serviceable parts of waste accumulators
-
- 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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
-
- 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
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- 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
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Composite Materials (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention belongs to the field of waste electrode material recovery and electrode material preparation, and particularly relates to a nickel-cobalt-manganese multi-metal @ graphitized carbon @ hierarchical porous carbon material and a method for preparing the nickel-cobalt-manganese multi-metal @ graphitized carbon @ hierarchical porous carbon material through a waste positive electrode material. The nanometer pore channels in the carbon material are communicated with each other, the material is locally graphitized by transition metal catalysis, meanwhile, the highly dispersed nickel, cobalt and manganese are embedded in the material, so that rich reaction interfaces and lithium ion transmission channels are provided, the polarity of the carbon substrate can be improved by the multi-metal doped porous carbon, the metal particles catalyze the conversion of polysulfide, and further the discharge specific capacity, the multiplying power and the cycle performance of the lithium sulfur battery prepared from the anode active material are remarkably improved.
Description
Technical Field
The invention relates to the field of battery electrode material preparation, in particular to a material for a lithium-sulfur battery anode.
Background
With the increase of energy demand and the continuous development of the electronic market and the electric vehicle market, the lithium ion battery is favored by people due to the advantages of safety, environmental protection, higher specific energy, good electrochemical performance and the like. As such, a large number of lithium ion batteries are produced and consumed. In order to protect the environment, save resources and recycle resources, it is necessary to develop a waste lithium ion battery recycling technology. And the lithium ion anode ternary material contains various valuable metal elements and has a high recovery value. However, the traditional wet recovery process is relatively expensive, and how to efficiently recover valuable elements or treat and recycle wastes at low cost has led to extensive research.
What occurs in the anode is intercalation and deintercalation of lithium ions in the graphite anode unlike in the conventional lithium ion battery; the charge and discharge process of the lithium metal battery anode is the dissolution and deposition process of lithium metal; the basic reaction formula is as follows: charging of Li++ e ═ Li; discharge Li-e ═ Li+. Lithium-sulfur batteries, which are typical lithium metal batteries, have attracted extensive research interest due to their outstanding advantages of high energy density and low cost, but are produced byLithium sulfur batteries still face challenges such as low sulfur utilization, short cycle life and limited power density due to poor conductivity of sulfur and lithium sulfide, shuttling effect of lithium polysulfide, and large volume change of active species during slow conversion kinetics and cycling. Through continuous efforts, people develop strategies such as physical confinement, chemical adsorption of lithium polysulfide and the like, so that shuttle effect, polarization effect and volume effect existing in the lithium-sulfur battery are inhibited to a certain extent, and the utilization rate, rate capability and cycling stability of sulfur are improved. However, the industrialization process of the lithium-sulfur battery is faced with the severe problems of high sulfur-carrying capacity and low liquid-sulfur ratio. Accelerating polysulfide conversion under severe conditions with a suitable catalyst is a viable approach.
Disclosure of Invention
In order to overcome the defects of the prior art, the first object of the invention is to provide a nickel-cobalt-manganese multi-metal @ graphitized carbon @ hierarchical porous carbon material (also referred to as a carbon material in the invention), and the invention aims to provide a material which is applicable to a lithium-sulfur battery and can improve the electrical properties of the lithium-sulfur battery.
The second purpose of the invention is to provide a preparation method of the nickel-cobalt-manganese multi-metal @ graphitized carbon @ hierarchical porous carbon material.
The third purpose of the invention is to provide an application of the nickel-cobalt-manganese polymetal @ graphitized carbon @ hierarchical porous carbon material.
The fourth purpose of the invention is to provide a lithium-sulfur battery positive electrode active material obtained by loading sulfur in the nickel-cobalt-manganese multi-metal @ graphitized carbon @ hierarchical porous carbon material.
The fifth purpose of the invention is to provide a preparation method of the positive electrode active material of the lithium-sulfur battery.
The sixth purpose of the invention is to provide the application of the composite positive electrode active material in a lithium-sulfur battery.
A seventh object of the present invention is to provide a lithium-sulfur battery to which the composite positive electrode active material is added.
A nickel-cobalt-manganese polymetallic @ graphitized carbon @ hierarchical pore porous carbon material comprises amorphous carbon with a hierarchical pore structure, wherein a plurality of active particles are dispersed in situ in a skeleton of the amorphous carbon; the active particles comprise graphitized carbon and ternary metal simple substances of nickel, cobalt and manganese embedded in the graphitized carbon in situ.
The carbon material has a hierarchical pore structure, and double in-situ composite active particles of nickel-cobalt-manganese ternary metal @ graphitized carbon are dispersed and distributed in situ in an amorphous carbon framework of the carbon material. Researches show that the special hierarchical holes, the double in-situ dispersion distribution morphology and the synergistic property of the nickel-cobalt-manganese ternary metal can unexpectedly show excellent polysulfide catalytic performance in the lithium-sulfur battery, and can show excellent multiplying power, capacity and cycle performance in the lithium-sulfur battery.
The holes in the carbon material are template etching level holes formed by waste ternary materials. The hierarchical pores are nano-hierarchical pores (the pore diameter is 1-1000 nm). Conductivity of 103～105S·m-1. The specific surface area of the porous carbon material is 1000-2500 m2(ii)/g; preferably 1500 to 2000m2(ii) in terms of/g. The total pore volume is 0.5-3 cm3(ii) in terms of/g. The wall thickness of the carbon hole is 0.2-7 nm. The pore diameter is 10-500 nm.
The carbon material has active particles with local graphitized structures dispersed in situ.
Preferably, the carbon material is represented by formula ID/IG0.2 to 2; preferably 0.8 to 1.
The invention innovatively finds that under the hierarchical pore and local graphitization morphology, the coordination of the ternary metals of nickel, cobalt and manganese is matched, so that the catalytic effect of the material on polysulfide is further improved, and the performance of the material in a lithium-sulfur battery is further improved.
In the invention, the nickel, the cobalt and the manganese can be dispersed in different active particles independently, or any two or three of the nickel, the cobalt and the manganese can be dispersed in the same active particle.
Preferably, the total content of the ternary metal simple substances of nickel, cobalt and manganese is 0.5-10 atm%; preferably 1 to 2.5 atm%. The cycling stability of the material under the preferred conditions is better.
A method for preparing the nickel-cobalt-manganese polymetallic @ graphitized carbon @ hierarchical porous carbon material by using a waste nickel-cobalt-manganese ternary material comprises the following steps:
(1) stripping to obtain a waste nickel-cobalt-manganese ternary cathode material, and then oxidizing and roasting to obtain micron spherical waste NCM cathode active material particles;
(2) ball-milling the waste NCM positive electrode active material particles obtained in the step (1) in dilute acid A with the concentration of not higher than 0.5M at the rotating speed of 150-500 rpm, and then adding a surfactant to obtain a dispersion liquid dispersed with waste NCM ternary active material nanospheres;
(3) adding a carbon source into the nanosphere dispersion liquid obtained in the step (2), drying the nanosphere dispersion liquid after forming slurry, carbonizing the nanosphere dispersion liquid at the temperature of 800-1200 ℃, and etching the waste NCM active material nanosphere template in acid liquid B with the concentration not higher than 1M to obtain the nickel-cobalt-manganese polymetal @ graphitized carbon @ hierarchical porous carbon material.
The waste nickel-cobalt-manganese ternary positive electrode material is a nickel-cobalt-manganese eutectic oxide solid waste, and the existing recovery mainly adopts a liquid phase recovery concept of leaching, extracting and the like. The invention innovatively utilizes the solid waste characteristic of the waste nickel-cobalt-manganese ternary positive electrode material, and directly recovers and prepares the high-performance lithium-sulfur battery material by a solid recovery idea.
The preparation method comprises the steps of innovatively ball-milling the stripped waste active material in advance under the condition of the step (2), carrying out chemical-physical double modification, then using the modified waste active material as a grading template in a carbonization stage with the assistance of a surfactant to realize the in-situ formation of hierarchical template pore-forming, metal hybridization and local graphitization in the carbonization process, and obtaining the hierarchical pore, local double in-situ graphitization structure and nickel-cobalt-manganese ternary doped carbon material by simply removing the nano-sphere template of the waste NCM active material.
The invention firstly provides a method for preparing a lithium-sulfur battery material crossing the technical field by recovering waste ternary materials. The nickel-cobalt-manganese oxide eutectic solid characteristic of the waste ternary material is used as a hierarchical template for the first time, so that the pore forming of the carbon material is realized, and in-situ nickel-cobalt-manganese synchronous synergistic hybridization and local graphitization are performed on the carbon material; thereby recycling and preparing the high-performance lithium-sulfur battery material.
The inventor of the invention also finds that, by adopting the waste ternary material after long-term cycle retirement, the long-term cycle reaction, the surface SEI component characteristic and the surface structure characteristic of the waste ternary material enable the waste ternary material to unexpectedly provide more reaction sites for the lithium-sulfur positive active material obtained by recovery and co-production compared with the non-cycle material, and the first-cycle discharge capacity, the coulombic efficiency and other performances of the obtained carbon material in the lithium-sulfur battery can be further improved unexpectedly.
According to the preparation method provided by the invention, under the process conditions, the preparation parameters of each step are further matched, so that the lithium-sulfur battery active material with high capacity and high cycle performance can be obtained unexpectedly.
In the invention, the existing method can be adopted for the processes of disassembling, stripping, crushing and the like of the waste ternary material.
In the invention, the anode material obtained by stripping and crushing is oxidized and roasted to obtain micron particles.
Preferably, the chemical formula of the waste NCM positive electrode active material is LiNi0.5Co0.2Mn0.3O2、LiNi0.6CoMn0.2O2、LiNi0.8Co0.1Mn0.1O2、LiNi1/3Co1/3Mn1/3O2。
The temperature of oxidizing roasting is 300-900 ℃.
The particle size of the micron spherical waste NCM positive active material is 3-15 microns.
According to the technical scheme, the waste NCM positive electrode active material is innovatively subjected to ball milling in the dilute acid A, physical and chemical double modification is carried out, and a surfactant is added to obtain a dispersion liquid in which nano-scale particles of the waste NCM positive electrode active material are dispersed.
Researches show that the concentration of the acid liquid A and the control of the ball milling speed and time are further cooperated with the structure of the waste ternary material and the material characteristics of long-term circulation, so that the subsequent lithium-sulfur battery positive active material with excellent performance can be further prepared.
Preferably, the diluted acid A is at least one acid solution of hydrochloric acid, nitric acid and sulfuric acid.
In the invention, the acid solution A is a dilute acid solution. Preferably, the concentration of the acid in the acid solution A is 0.001-0.1M; preferably 0.01 to 0.02M.
Preferably, the ball milling speed is 150-350 rpm. The ball milling time is 1-10 h.
The solid-to-liquid ratio of the acid liquid A to the waste NCM positive electrode active material particles is 0.1-10.
The diameter of the nano spherical particles is 1-1000 nm.
The surfactant is one or more of CTAB, PVP, CTAB and SDS;
in the nanoparticle dispersion liquid, the content of the surfactant is 0.1-1 wt%.
In the invention, the dispersion liquid and the carbon source are innovatively mixed and carbonized, and hierarchical pore-forming, nickel-cobalt-manganese ternary synergistic doping and local graphitization are realized under the action of a grading template of waste ternary nanoparticles in the dispersion liquid.
The carbon source is one or more of sucrose, starch and polydopamine.
The carbonization temperature is preferably 1000-1200 ℃.
The present inventors have discovered that the use of dilute acid for the template etch unexpectedly improves the properties of the resulting material.
The acid solution B is one or more of sulfuric acid, hydrochloric acid and nitric acid, and the concentration of the acid solution B is 0.05-0.5M; more preferably 0.01 to 0.02M.
The etching process is carried out under the condition of stirring for 1-10 h at normal temperature (for example, 15-40 ℃).
The invention relates to a preferable preparation method, which comprises the following steps:
(1) and (3) stripping the waste ternary positive electrode material from the current collector, drying, crushing, and firing the crushed powder in an oxygen atmosphere to remove residual solvent, binder and conductive carbon black in the material to obtain the micron spherical particles.
(2) And (2) adding a certain amount of dilute acid into the micron spherical particles obtained in the step (1) and treating under high-energy stirring to obtain nano spherical particles, and adding a certain amount of surfactant when the pH of the solution is close to neutral to obtain the ternary nanosphere dispersion.
(3) And (3) mixing a certain amount of carbon source with the nanosphere dispersion liquid obtained in the step (2), forming slurry, drying and carbonizing, and removing the ternary nano template by acid washing to obtain the multi-element doped porous carbon material.
The invention also comprises the carbon material prepared by the preparation method.
The invention also provides application of the nickel-cobalt-manganese multi-metal @ graphitized carbon @ hierarchical porous carbon material, and the nickel-cobalt-manganese multi-metal @ graphitized carbon @ hierarchical porous carbon material is used as a positive active material of a lithium-sulfur battery after being loaded with sulfur.
Preferred use thereof for the preparation of a positive electrode material for a lithium-sulfur battery.
Further preferred use is for the preparation of a positive electrode for a lithium-sulphur battery.
A further preferred use is in the preparation of a lithium-sulphur battery.
The invention also provides a lithium-sulfur battery composite positive electrode active material which comprises the nickel-cobalt-manganese polymetal @ graphitized carbon @ hierarchical porous carbon material and an elemental sulfur source.
Preferably, the elemental sulfur source is sublimed sulfur or polymeric sulfur.
Preferably, the sulfur carrying amount of the composite positive electrode active material is 60-80 wt%.
The composite cathode active material can adopt the existing method to fill a simple substance sulfur source into the nickel-cobalt-manganese multi-metal @ graphitized carbon @ hierarchical porous carbon material; for example, sulfur may be carried by sublimation of sulfur, or the polymerized sulfur may be filled by in situ polymerization of elemental sulfur.
The conductive agent and the adhesive can adopt materials which have conductive or adhesive functions and are available in the industry. The content of the components can be adjusted according to the use requirement.
Preferably, in the positive electrode material, the content of the conductive agent is 5-10%; the content of the binder is 5-10%.
The preparation method of the cathode material can adopt the conventional method, for example, the composite active material, the conductive agent and the binder are slurried by a solvent, coated and dried to obtain the cathode material.
The invention also provides a lithium-sulfur battery positive electrode which comprises a current collector and the positive electrode material compounded on the surface of the current collector.
The invention also provides a lithium-sulfur battery, wherein the composite positive electrode active material is compounded in the positive electrode of the lithium-sulfur battery.
The invention also provides a lithium-sulfur battery, and the material of the positive electrode of the lithium-sulfur battery comprises the positive electrode.
Compared with the prior art, the invention has the beneficial effects that:
(1) the carbon material has hierarchical pores, is compounded with nickel, cobalt and manganese ternary metals in situ, and is locally graphitized. Researches show that transition metal elements of nickel, cobalt and manganese with high catalytic activity are highly dispersed in the porous carbon material with the hierarchical pore structure, so that the reaction energy barrier of the lithium-sulfur battery in the charging and discharging process can be obviously reduced, polysulfide conversion is accelerated, and the rate capability and the cycle stability of the lithium-sulfur battery are improved.
(2) The method provides the waste nickel-cobalt-manganese ternary solid waste as the solid waste of the waste lithium ion battery for the first time. The invention discloses a lithium-sulfur battery, which belongs to the field of lithium metal batteries, and provides and realizes the preparation of a material of the lithium-sulfur battery in the battery crossing field by using waste nickel-cobalt-manganese ternary solid wastes for the first time;
(3) the invention firstly utilizes the solid characteristic recovery idea of the waste nickel-cobalt-manganese ternary solid waste. The method is used as a graded solid template to participate in the carbonization step, and hierarchical pore preparation, nickel-cobalt-manganese ternary synchronous in-situ doping and local graphitization are realized by controlling the preparation parameters, so that not only is the effective recovery of solid wastes realized, but also a material which has brand new performance, excellent polysulfide catalytic performance and excellent electrical performance in a lithium-sulfur battery is unexpectedly obtained;
(4) research shows that the long-cycle characteristic of the waste nickel-cobalt-manganese ternary solid waste can be utilized under the method disclosed by the invention, and the performance of the obtained material in a lithium-sulfur battery can be further improved unexpectedly.
(5) The multifunctional synergistic effect of the composite material can obviously improve the electrochemical performance of the lithium-sulfur battery, and the material is suitable for large-scale industrial production and provides a method for the industrial application of the lithium-sulfur battery.
Drawings
FIG. 1 is an SEM image of a multi-metallic element doped porous carbon material prepared in example 1;
fig. 2 is a TG diagram of the multi-metallic element doped porous carbon/sulfur composite positive electrode material prepared in example 1;
fig. 3 is a cycle chart of the multi-metallic element doped porous carbon/sulfur composite cathode material prepared in example 1.
FIG. 4 is a Raman diagram of the multi-metallic element-doped porous carbon material prepared in example 1.
Detailed Description
The present invention will be described in further detail with reference to examples, but the present invention is not limited to the scope of the present invention.
In the following cases, the dilute acids are, unless otherwise stated, hydrochloric acid
The contents of nickel, cobalt and manganese are calculated by atomic percentage.
Example 1
Waste ternary power battery LiNi0.5Co0.2Mn0.3O2And (3) disassembling, taking out the positive electrode side, stripping the ternary active substance from the current collector, drying, crushing, carrying out heat treatment on 4 kg of crushed powder for 3 hours at 600 ℃ in an oxygen atmosphere, adding 20L0.01M diluted acid into the obtained powder, carrying out high-energy stirring at 350rpm for 5 hours to obtain nano spherical particles, measuring the main particle size by using a laser, wherein the range of the main particle size is 10-200 nm, and adding 50g of PVP when the pH of the solution is close to neutral to obtain the ternary nanosphere dispersion liquid. 5 kg of ternary nanosphere dispersion liquid is mixed with 5 kg of starch, and the mixture is uniformly stirred in a planet ball mill, wherein the stirring temperature is controlled at 80 ℃. Mixing the slurryDrying at 120 ℃, and carbonizing for 3 hours at 1200 ℃ in a nitrogen carbonization furnace; and crushing and screening the product, washing the ternary nano template by using 0.1M hydrochloric acid (the time is 3 hours), filtering and drying. The obtained local graphitized porous carbon material has rich pore channel structures and nickel, cobalt and manganese particles are embedded in the carbon material. The pore volume of the material is 2.04cm3(ii)/g, specific surface area 1757m2The pore diameter is mainly concentrated in the range of 10-200 nm, the carbon pore wall thickness is 0.21-4.95 nm, the total content of nickel, cobalt and manganese is 2.1 percent, ID/IG0.98, the four-probe method measured the electronic conductivity to be 103S·m-1. The method comprises the steps of ball-milling and mixing a multi-metal element doped porous carbon material and sulfur powder at a mass ratio of 2:8 for 2 hours at a high speed, heating to 155-190 ℃ under the protection of argon, preserving heat for 24 hours to obtain the multi-metal element doped porous carbon/sulfur composite cathode material, and obtaining the actual sulfur content of 77.5 wt% through thermogravimetric testing.
The composite positive electrode material obtained in example 1, conductive carbon black and polyvinylidene fluoride (PVDF) are uniformly mixed according to the mass ratio of 8:1:1, and are dispersed in NMP with a certain mass to prepare slurry (the solid content is 80 wt%), and then the slurry is coated on an aluminum foil current collector and is dried in vacuum at the temperature of 60 ℃ to obtain the lithium-sulfur battery positive electrode sheet. The battery assembly and testing was: punching the positive plate into an electrode plate with the diameter of 10mm, taking a metal lithium plate as a negative electrode, and taking 1M LiTFSI/DOL (dimethyl Ether) (1:1) +2 percent LiNO as electrolyte3And assembled into a CR2025 button cell in a glove box filled with argon. And carrying out constant-current charge and discharge tests at room temperature (25 ℃) at a current density of 0.5C (837mAh/g), wherein the charge and discharge cut-off voltage is 1.7-2.8V. The initial discharge specific capacity is 1268mAh/g, and the specific capacity is kept 1034mAh/g after 100 times of circulation.
Example 2
Compared with the embodiment 1, the difference is only that the waste ternary power battery LiNi is adopted0.6Co0.2Mn0.2O2The battery is treated, and specifically:
waste ternary power battery LiNi0.6Co0.2Mn0.2O2Disassembling, taking out the positive electrode side, stripping the ternary active material from the current collector, drying, crushing, and crushing 4 kg of crushed powderAnd (3) carrying out heat treatment for 3 hours at 600 ℃ in an oxygen atmosphere, adding a certain amount of 0.01M diluted acid (20L) into the obtained powder, carrying out high-energy stirring at 350rpm for 5 hours to obtain nano spherical particles, and adding 50g of PVP when the pH of the solution is close to neutral to obtain the ternary nanosphere dispersion. 5 kg of ternary nanosphere dispersion liquid is mixed with 5 kg of starch, and the mixture is uniformly stirred in a planet ball mill, wherein the stirring temperature is controlled at 80 ℃. Drying the slurry at 120 ℃, and carbonizing the slurry for 3 hours at 1200 ℃ in a nitrogen carbonization furnace; and crushing and screening the product, washing the ternary nano template by using 0.1M hydrochloric acid (the time is 3 hours), filtering and drying. The obtained local graphitized porous carbon material has rich pore channel structures and nickel, cobalt and manganese particles are embedded in the carbon material. The pore volume of the material is 1.98cm3Per g, specific surface area 1658m2The pore diameter is mainly concentrated in the range of 10-150 nm, the carbon pore wall thickness is 0.24-5.67 nm, and the total content of nickel, cobalt and manganese is 1.9%. The method comprises the steps of ball-milling and mixing a multi-metal element doped porous carbon material and sulfur powder at a mass ratio of 2:8 for 2 hours at a high speed, heating to 155-190 ℃ under the protection of argon, preserving heat for 24 hours to obtain the multi-metal element doped porous carbon/sulfur composite cathode material, and obtaining the actual sulfur content of 78.1 wt% through thermogravimetric testing.
The composite positive electrode material obtained in example 2, conductive carbon black and polyvinylidene fluoride (PVDF) are uniformly mixed according to the mass ratio of 8:1:1, and are dispersed in NMP with a certain mass to prepare slurry (the solid content is 80 wt%), and then the slurry is coated on an aluminum foil current collector and is dried in vacuum at 60 ℃ to obtain the lithium-sulfur battery positive electrode sheet. The battery assembly and testing was: punching the positive plate into an electrode plate with the diameter of 10mm, taking a metal lithium plate as a negative electrode, and taking 1M LiTFSI/DOL (dimethyl Ether) (1:1) +2 percent LiNO as electrolyte3And assembled into a CR2025 button cell in a glove box filled with argon. And carrying out constant-current charge and discharge tests at room temperature (25 ℃) at a current density of 0.5C (837mAh/g), wherein the charge and discharge cut-off voltage is 1.7-2.8V. The first discharge specific capacity is 1259mAh/g, and the specific capacity is 1046mAh/g after 100 times of circulation.
Example 3
Compared with the embodiment 1, the difference is only that the waste ternary power battery LiNi is adopted1/3Co1/3Mn1/3O2Battery proceeding placeThe method specifically comprises the following steps:
waste ternary power battery LiNi1/3Co1/3Mn1/3O2And (3) disassembling, taking out the positive electrode side, stripping the ternary active substance from the current collector, drying, crushing, carrying out heat treatment on 4 kg of crushed powder at 600 ℃ for 3 hours in an oxygen atmosphere, adding a certain amount of 0.01M dilute acid (20L) into the obtained powder, carrying out high-energy stirring at 350rpm for 5 hours to obtain nano spherical particles, and adding 50g of PVP when the pH of the solution is close to neutrality to obtain the ternary nanosphere dispersion liquid. 5 kg of ternary nanosphere dispersion is mixed with 5 kg of starch, and the mixture is uniformly stirred in a planetary ball mill, wherein the stirring temperature is controlled at 80 ℃. Drying the slurry at 120 ℃, and carbonizing the slurry for 3 hours at 1200 ℃ in a nitrogen carbonization furnace; and crushing and screening the product, washing the ternary nano template by using 0.1M hydrochloric acid (the time is 3 hours), filtering and drying. The obtained local graphitized porous carbon material has rich pore channel structures and nickel, cobalt and manganese particles are embedded in the carbon material. The pore volume of the material is 1.85cm3Per g, specific surface area 1586m2The pore diameter is mainly concentrated in the range of 10-150 nm, the carbon pore wall thickness is 0.23-4.86 nm, and the total content of nickel, cobalt and manganese is 1.6%. The method comprises the steps of ball-milling and mixing a multi-metal element doped porous carbon material and sulfur powder at a mass ratio of 2:8 for 2 hours at a high speed, heating to 155-190 ℃ under the protection of argon, preserving heat for 24 hours to obtain the multi-metal element doped porous carbon/sulfur composite cathode material, and obtaining the actual sulfur content of 79.2 wt% through thermogravimetric testing.
The composite positive electrode material obtained in example 3, conductive carbon black and polyvinylidene fluoride (PVDF) are uniformly mixed according to the mass ratio of 8:1:1, and are dispersed in NMP with a certain mass to prepare slurry (the solid content is 80 wt%), and then the slurry is coated on an aluminum foil current collector and is dried in vacuum at 60 ℃ to obtain the lithium-sulfur battery positive electrode sheet. The battery assembly and testing was: punching the positive plate into an electrode plate with the diameter of 10mm, taking a metal lithium plate as a negative electrode, and taking 1M LiTFSI/DOL (dimethyl Ether) (1:1) +2 percent LiNO as electrolyte3And assembled into a CR2025 button cell in a glove box filled with argon. And carrying out constant-current charge and discharge tests at room temperature (25 ℃) at a current density of 0.5C (837mAh/g), wherein the charge and discharge cut-off voltage is 1.7-2.8V. The first discharge specific capacity is 1272mAh/g, 100 times of circulationThe specific capacity after the ring is kept to be 1086 mAh/g.
Example 4
Compared with the embodiment 1, the difference is only that the waste ternary power battery LiNi is adopted0.8Co0.1Mn0.1O2The battery is treated, and specifically:
waste ternary power battery LiNi0.8Co0.1Mn0.1O2And (3) disassembling, taking out the positive electrode side, stripping the ternary active substance from the current collector, drying, crushing, carrying out heat treatment on 4 kg of crushed powder at 600 ℃ for 3 hours in an oxygen atmosphere, adding a certain amount of 0.01M dilute acid (20L) into the obtained powder, carrying out high-energy stirring at 350rpm for 5 hours to obtain nano spherical particles, and adding 50g of PVP when the pH of the solution is close to neutrality to obtain the ternary nanosphere dispersion liquid. 5 kg of ternary nanosphere dispersion is mixed with 5 kg of starch, and the mixture is uniformly stirred in a planetary ball mill, wherein the stirring temperature is controlled at 80 ℃. Drying the slurry at 120 ℃, and carbonizing the slurry for 3 hours at 1200 ℃ in a nitrogen carbonization furnace; and crushing and screening the product, washing the ternary nano template by using 0.1M hydrochloric acid (the time is 3 hours), filtering and drying. The obtained local graphitized porous carbon material has rich pore channel structures and nickel, cobalt and manganese particles are embedded in the carbon material. The pore volume of the material is 1.79cm3Per g, specific surface area 1616m2The pore diameter is mainly concentrated in the range of 10-150 nm, the carbon pore wall thickness is 0.24-4.67 nm, and the total content of nickel, cobalt and manganese is 1.4%. The method comprises the steps of ball-milling and mixing a multi-metal element doped porous carbon material and sulfur powder at a mass ratio of 2:8 for 2 hours at a high speed, heating to 155-190 ℃ under the protection of argon, preserving heat for 24 hours to obtain the multi-metal element doped porous carbon/sulfur composite cathode material, and obtaining the actual sulfur content of 78.6 wt% through thermogravimetric testing.
The composite positive electrode material obtained in example 4, conductive carbon black and polyvinylidene fluoride (PVDF) were uniformly mixed in a mass ratio of 8:1:1, and dispersed in NMP of a certain mass to prepare a slurry (solid content is 80 wt%), and then coated on an aluminum foil current collector, and vacuum-dried at 60 ℃ to obtain a lithium-sulfur battery positive electrode sheet. The battery assembly and testing was: punching the positive plate into an electrode plate with the diameter of 10mm, taking a metal lithium plate as a negative electrode, and taking 1M Li as electrolyteTFSI/DOL:DME(1:1)+2％LiNO3And assembled into a CR2025 button cell in a glove box filled with argon. And carrying out constant-current charge and discharge tests at room temperature (25 ℃) at a current density of 0.5C (837mAh/g), wherein the charge and discharge cut-off voltage is 1.7-2.8V. The first discharge specific capacity is 1285mAh/g, and the specific capacity is kept 1068mAh/g after 100 times of circulation.
Example 5
Compared with the example 1, the difference is mainly that the high-energy stirring time is 3 hours, the carbonization temperature is 800 ℃, and specifically:
waste ternary power battery LiNi0.5Co0.2Mn0.3O2And (3) disassembling, taking out the positive electrode side, stripping the ternary active substance from the current collector, drying, crushing, carrying out heat treatment on 4 kg of crushed powder at 600 ℃ for 3 hours in an oxygen atmosphere, adding a certain amount of 0.01M dilute acid (20L) into the obtained powder, carrying out high-energy stirring at 350rpm for 3 hours to obtain nano spherical particles, and adding 50g of PVP when the pH of the solution is close to neutrality to obtain the ternary nanosphere dispersion liquid. 5 kg of ternary nanosphere dispersion is mixed with 5 kg of starch, and the mixture is uniformly stirred in a planetary ball mill, wherein the stirring temperature is controlled at 80 ℃. Drying the slurry at 120 ℃, and carbonizing the slurry for 3 hours at 800 ℃ in a nitrogen carbonization furnace; and crushing and screening the product, washing the ternary nano template by using 0.1M hydrochloric acid (the time is 3 hours), filtering and drying. The obtained local graphitized porous carbon material has rich pore channel structures and nickel, cobalt and manganese particles are embedded in the carbon material. The pore volume of the material is 1.91cm3Per g, specific surface area 1514m2The pore diameter is mainly concentrated in the range of 10-200 nm, the carbon pore wall thickness is 0.23-4.86 nm, and the total content of nickel and cobalt manganese is 1.5%. The method comprises the steps of ball-milling and mixing a multi-metal element doped porous carbon material and sulfur powder at a mass ratio of 2:8 for 2 hours at a high speed, heating to 155-190 ℃ under the protection of argon, preserving heat for 24 hours to obtain the multi-metal element doped porous carbon/sulfur composite cathode material, and obtaining the actual sulfur content of 78.2 wt% through thermogravimetric testing.
The composite positive electrode material obtained in example 5, conductive carbon black, and polyvinylidene fluoride (PVDF) were uniformly mixed in a mass ratio of 8:1:1, and dispersed in a certain mass of NMP to prepare a slurry (solid content: 80 wt%), followed by coating on the slurryAnd (3) drying the aluminum foil current collector in vacuum at the temperature of 60 ℃ to obtain the lithium-sulfur battery positive plate. The battery assembly and testing was: punching the positive plate into an electrode plate with the diameter of 10mm, taking a metal lithium plate as a negative electrode, and taking 1M LiTFSI/DOL (dimethyl Ether) (1:1) +2 percent LiNO as electrolyte3And assembled into a CR2025 button cell in a glove box filled with argon. And carrying out constant-current charge and discharge tests at room temperature (25 ℃) at a current density of 0.5C (837mAh/g), wherein the charge and discharge cut-off voltage is 1.7-2.8V. The first discharge specific capacity is 1258mAh/g, and the specific capacity after 100 cycles is kept 1021mAh/g
Example 6
Compared with example 5, the difference is mainly that the temperature of the oxidizing roasting is reduced (300 ℃), and the rotating speed of the high-energy stirring is reduced (150rpm), and the specific steps are as follows:
waste ternary power battery LiNi0.5Co0.2Mn0.3O2And (3) disassembling, taking out the positive electrode side, stripping the ternary active substance from the current collector, drying, crushing, carrying out heat treatment on 4 kg of crushed powder for 3 hours at 300 ℃ in an oxygen atmosphere, adding a certain amount of 0.01M dilute acid (20L) into the obtained powder, carrying out high-energy stirring at 150rpm for 3 hours to obtain nano spherical particles, and adding 50g of PVP when the pH of the solution is close to neutral to obtain the ternary nanosphere dispersion liquid. 5 kg of ternary nanosphere dispersion is mixed with 5 kg of starch, and the mixture is uniformly stirred in a planetary ball mill, wherein the stirring temperature is controlled at 80 ℃. Drying the slurry at 120 ℃, and carbonizing the slurry for 3 hours at 800 ℃ in a nitrogen carbonization furnace; and crushing and screening the product, washing the ternary nano template by using 0.1M hydrochloric acid (the time is 3 hours), filtering and drying. The obtained local graphitized porous carbon material has rich pore channel structures and nickel, cobalt and manganese particles are embedded in the carbon material. The pore volume of the material is 2.14cm3(ii)/g, specific surface area of 1814m2The pore diameter is mainly concentrated in the range of 10-500 nm, the carbon pore wall thickness is 0.58-6.84 nm, and the total content of nickel and cobalt manganese is 1.5%. The method comprises the steps of ball-milling and mixing a multi-metal element doped porous carbon material and sulfur powder at a mass ratio of 2:8 for 2 hours at a high speed, heating to 155-190 ℃ under the protection of argon, preserving heat for 24 hours to obtain the multi-metal element doped porous carbon/sulfur composite cathode material, and obtaining the actual sulfur content of 79.1 wt% through thermogravimetric testing.
The composite positive electrode material obtained in example 6, conductive carbon black and polyvinylidene fluoride (PVDF) were uniformly mixed in a mass ratio of 8:1:1, and dispersed in NMP of a certain mass to prepare a slurry (solid content is 80 wt%), and then coated on an aluminum foil current collector, and vacuum-dried at 60 ℃ to obtain a lithium-sulfur battery positive electrode sheet. The battery assembly and testing was: punching the positive plate into an electrode plate with the diameter of 10mm, taking a metal lithium plate as a negative electrode, and taking 1M LiTFSI/DOL (dimethyl Ether) (1:1) +2 percent LiNO as electrolyte3And assembled into a CR2025 button cell in a glove box filled with argon. And carrying out constant-current charge and discharge tests at room temperature (25 ℃) at a current density of 0.5C (837mAh/g), wherein the charge and discharge cut-off voltage is 1.7-2.8V. The first discharge specific capacity is 1247mAh/g, and the specific capacity after 100 cycles is kept 986mAh/g
Example 7
Compared with the example 1, the difference is that the concentration of the dilute acid is 0.02M, and specifically:
waste ternary power battery LiNi0.5Co0.2Mn0.3O2And (3) disassembling, taking out the positive electrode side, stripping the ternary active substance from the current collector, drying, crushing, carrying out heat treatment on 4 kg of crushed powder for 3 hours at 600 ℃ under an oxygen atmosphere, adding 20L of diluted acid with a certain amount of 0.02M into the obtained powder, carrying out treatment for 5 hours under high-energy stirring at 350rpm (stirring condition), thus obtaining nano spherical particles, and adding 50g of PVP when the pH of the solution is close to neutral to obtain the ternary nanosphere dispersion liquid. 5 kg of ternary nanosphere dispersion liquid is mixed with 5 kg of starch, and the mixture is uniformly stirred in a planet ball mill, wherein the stirring temperature is controlled at 80 ℃. Drying the slurry 120, and carbonizing the slurry in a nitrogen carbonization furnace at 1200 ℃ for 3 hours; and crushing and screening the product, washing the ternary nano template by using 0.1M hydrochloric acid (the time is 3 hours), filtering and drying. The obtained local graphitized porous carbon material has rich pore channel structures and nickel, cobalt and manganese particles are embedded in the carbon material. The pore volume of the material is 1.65cm3G, specific surface area of 1557m2The pore diameter is mainly concentrated in the range of 5-100 nm, the carbon pore wall thickness is 0.31-5.68 nm, and the total content of nickel, cobalt and manganese is 2.2%. The multi-metal element doped porous carbon material and sulfur powder are mixed for 2 hours in a high-speed ball milling mode according to the mass ratio of 2:8, and then the mixture is subjected to ball millingUnder the protection of argon, heating to 155-190 ℃, and preserving heat for 24 hours to obtain the multi-metal element doped porous carbon/sulfur composite cathode material, wherein the actual sulfur content is 78.4 wt% through thermogravimetric test.
The composite positive electrode material obtained in example 7, conductive carbon black and polyvinylidene fluoride (PVDF) were uniformly mixed in a mass ratio of 8:1:1, and dispersed in NMP of a certain mass to prepare a slurry (solid content is 80 wt%), and then coated on an aluminum foil current collector, and vacuum-dried at 60 ℃ to obtain a lithium-sulfur battery positive electrode sheet. The battery assembly and testing was: punching the positive plate into an electrode plate with the diameter of 10mm, taking a metal lithium plate as a negative electrode, and taking 1M LiTFSI/DOL (dimethyl Ether) (1:1) +2 percent LiNO as electrolyte3And assembled into a CR2025 button cell in a glove box filled with argon. And carrying out constant-current charge and discharge tests at room temperature (25 ℃) at a current density of 0.5C (837mAh/g), wherein the charge and discharge cut-off voltage is 1.7-2.8V. The first discharge specific capacity is 1189mAh/g, the specific capacity after 100 cycles is kept 1021mAh/g, and the capacity retention rate of 85.9 percent is respectively maintained.
Comparative example 1
Compared with the embodiment 1, the solid-liquid separation treatment is carried out on the acid ball milling system, which comprises the following specific steps:
waste ternary power battery LiNi0.5Co0.2Mn0.3O2And (2) disassembling, taking out the positive electrode side, stripping the ternary active substance from the current collector, drying, crushing, carrying out heat treatment on 4 kg of crushed powder at 600 ℃ for 3 hours in an oxygen atmosphere, adding a certain amount of 0.01M dilute acid (20L) into the obtained powder, treating under high-energy stirring to obtain nano spherical particles, filtering and washing filter residues when the pH of the solution is close to neutrality, and adding 50g of PVP into the filter residues to obtain a ternary nanosphere dispersion liquid. 5 kg of ternary nanosphere dispersion liquid is mixed with 5 kg of starch, and the mixture is uniformly stirred in a planet ball mill, wherein the stirring temperature is controlled at 80 ℃. Drying the slurry 120, and carbonizing the slurry in a nitrogen carbonization furnace at 1200 ℃ for 3 hours; and crushing and screening the product, washing the ternary nano template by using 0.1M hydrochloric acid (the time is 3 hours), filtering and drying. Obtaining the porous carbon material with rich pore channel structures. The pore volume of the material is 2.17cm3Per g, specific surface area 1668m2The pore diameter is mainly concentrated in the range of 10-150 nm, and the carbon pore wall thickness is 0.48-5.12 nm. The porous carbon material and sulfur powder are subjected to high-speed ball milling and mixing for 2h according to the mass ratio of 2:8, then the temperature is raised to 155-190 ℃ under the protection of argon, the temperature is kept for 24h, the porous carbon/sulfur composite positive electrode material is obtained, and the actual sulfur content is 78.1 wt% through thermogravimetric testing.
And (2) uniformly mixing the composite positive electrode material obtained in the comparative example 1, conductive carbon black and polyvinylidene fluoride (PVDF) according to the mass ratio of 8:1:1, dispersing the mixture in NMP with a certain mass to prepare slurry (the solid content is 80 wt%), coating the slurry on an aluminum foil current collector, and drying the aluminum foil current collector in vacuum at the temperature of 60 ℃ to obtain the lithium-sulfur battery positive electrode plate. The battery assembly and testing was: punching the positive plate into an electrode plate with the diameter of 10mm, taking a metal lithium plate as a negative electrode, and taking 1M LiTFSI/DOL (dimethyl Ether) (1:1) +2 percent LiNO as electrolyte3And assembled into a CR2025 button cell in a glove box filled with argon. And carrying out constant-current charge and discharge tests at room temperature (25 ℃) at a current density of 0.5C (837mAh/g), wherein the charge and discharge cut-off voltage is 1.7-2.8V. The first discharge specific capacity is 1161mAh/g, the specific capacity after 100 cycles is kept 921mAh/g, and the capacity retention rate of 79.3 percent is respectively maintained.
In comparative example 1, the transition metal salt solution in the template dispersion liquid can be removed, and the prepared material has extremely low content of nickel, cobalt and manganese elements, is not beneficial to providing enough active sites for the lithium-sulfur battery to contact with polysulfide in the circulation process, and has extremely low catalytic action. Resulting in a material with low overall capacity and fast decay.
Comparative example 2
Waste ternary power battery LiNi0.5Co0.2Mn0.3O2And (3) disassembling, taking out the positive side, stripping the ternary active substance from the current collector, drying, crushing, carrying out heat treatment on 4 kg of crushed powder at 600 ℃ for 3 hours in an oxygen atmosphere, adding a certain amount of 0.01M dilute acid (20L) into the obtained powder, treating under high-energy stirring to obtain nano spherical particles, and adding 50g of PVP when the pH of the solution is close to neutrality to obtain the ternary nanosphere dispersion liquid. Mixing 5 kg of ternary nanosphere dispersion liquid with 5 kg of starch, uniformly stirring in a planetary ball mill, and stirring at a certain temperatureThe temperature is controlled at 80 degrees celsius. Drying the slurry 120, and carbonizing the slurry in a nitrogen carbonization furnace at 1200 ℃ for 3 hours; and crushing and screening the product, washing the ternary nano template by using 1.5M hydrochloric acid (acid solution B) (the time is 3 hours), filtering and drying. Obtaining the local graphitized porous carbon material with rich pore channel structures. The pore volume of the material is 2.29cm3Per g, specific surface area of 1747m2The pore diameter is mainly concentrated in the range of 10-150 nm, the carbon pore wall thickness is 0.29-4.68 nm, and the total content of nickel and cobalt manganese is 0.001%. The porous carbon material and sulfur powder are subjected to high-speed ball milling and mixing for 2h according to the mass ratio of 2:8, then the temperature is raised to 155-190 ℃ under the protection of argon, the temperature is kept for 24h, the porous carbon/sulfur composite positive electrode material is obtained, and the actual sulfur content is 77.2 wt% through thermogravimetric testing.
And (3) uniformly mixing the composite positive electrode material obtained in the comparative example 2, conductive carbon black and polyvinylidene fluoride (PVDF) according to the mass ratio of 8:1:1, dispersing the mixture in NMP with a certain mass to prepare slurry (the solid content is 80 wt%), coating the slurry on an aluminum foil current collector, and drying the aluminum foil current collector in vacuum at the temperature of 60 ℃ to obtain the lithium-sulfur battery positive electrode plate. The battery assembly and testing was: punching the positive plate into an electrode plate with the diameter of 10mm, taking a metal lithium plate as a negative electrode, and taking 1M LiTFSI/DOL (dimethyl Ether) (1:1) +2 percent LiNO as electrolyte3And assembled into a CR2025 button cell in a glove box filled with argon. And carrying out constant-current charge and discharge tests at room temperature (25 ℃) at a current density of 0.5C (837mAh/g), wherein the charge and discharge cut-off voltage is 1.7-2.8V. The initial discharge specific capacity is 1145mAh/g, the specific capacity is 829mAh/g after 100 cycles, and 72.4 percent of capacity retention rate is respectively maintained.
Compared with the example 1, the content of nickel, cobalt and manganese in the material can be reduced in the process of washing the template by adopting high-concentration strong acid, which is not beneficial to exerting the adsorption catalytic conversion function in the circulation process, and the capacity of the battery is reduced quickly.
Comparative example 3
The embodiment of comparative example 3 corresponds to that of example 5 except that the temperature for carbonizing the carbon material was reduced to 700 c, and the discharge capacity was 1108mAh/g at the first cycle and 814mAh/g after 100 cycles as compared with the experimental results.
Comparative example 4
The implementation route of comparative example 4 adopts the technical route of example 6, except that the surfactant PVP is not added in the raw materials, and experiments show that in the case of not adding the surfactant, the template and the carbon source are not uniformly dispersed, so that the wrapping property of the whole material is not good, and the uniformity of the porous structure in the high-temperature carbonized carbon material is difficult to maintain. This will seriously affect the sulfur carrying performance of the material for use in lithium sulfur batteries. The discharge capacity at the first circle is 1013mAh/g, and the discharge capacity after 100 circles is 751 mAh/g.
Comparative example 5
The implementation route of comparative example 5 adopts the technical route of example 1, except that the ternary cathode material disassembled from the waste battery is not used as the raw material, but the material which is not recycled (LiNi)0.5Co0.2Mn0.3O2) The method is directly applied to an implementation route, and the results of comparative tests show that the oxide spheres with hierarchical particle sizes are difficult to obtain when the materials are treated by acid because the electrolyte does not permeate the surfaces of the materials, so that the materials do not have hierarchical pore structures. Finally, the prepared material is not ideal for the whole capacity exertion of the composite anode material applied to the lithium-sulfur battery, the discharge capacity of the first circle is 1054mAh/g, and the discharge capacity of the first circle is 839mAh/g after 100 circles.
Comparative example 6
The implementation route of comparative example 6 adopts the technical route of example 6, except that the rotating speed is adjusted from 150rpm to 100rpm during the high-energy ball milling. The performance measurement was carried out under the same conditions as in example 6, and the results were: the first circle of discharge capacity is 985mAh/g, and the discharge capacity after 100 circles is 765 mAh/g.
Comparative example 7
The implementation route of comparative example 7 adopts the technical route of example 5, only the ball milling time is increased from 3 hours to 12 hours during high-energy ball milling, and the results of comparative experiments show that the overall material structure is seriously thinned due to longer ball milling time, and the obtained oxide template has smaller particle size. The porous carbon material prepared by applying the template has a poor porous structure. Finally, the prepared material is applied to a lithium-sulfur battery, the whole pore volume of the material is difficult to cope with the harsh condition of high sulfur loading, and elemental sulfur cannot enter the pore structure of the material under the condition of high sulfur loading, so that the content of the positive electrode material cannot be combined with a carbon substrate, and the material capacity is low. The overall capacity exertion of the composite anode material is not ideal, the first-circle discharge capacity is 931mAh/g, and the discharge capacity after 100 circles is 724 mAh/g.
Claims (10)
1. The nickel-cobalt-manganese polymetallic @ graphitized carbon @ hierarchical porous carbon material is characterized by comprising amorphous carbon with a hierarchical pore structure, wherein active particles are dispersed in situ in a skeleton of the amorphous carbon; the active particles comprise graphitized carbon and ternary metal simple substances of nickel, cobalt and manganese embedded in the graphitized carbon in situ.
2. The nickel-cobalt-manganese polymetallic @ graphitized carbon @ hierarchical porous carbon material of claim 1, wherein the specific surface area of the porous carbon material is 1000 to 2500m2(ii) a total pore volume of 0.5 to 3cm3The carbon wall thickness is 0.2-7 nm.
3. The nickel-cobalt-manganese multi-metal @ graphitized carbon @ hierarchical porous carbon material of claim 1, wherein the total content of the ternary metal simple substances of nickel, cobalt and manganese is 0.5 to 10 atm%; preferably 1 to 2.5 atm%.
4. A method for preparing the nickel-cobalt-manganese polymetallic @ graphitized carbon @ hierarchical porous carbon material disclosed by any one of claims 1 to 3 by using a waste nickel-cobalt-manganese ternary material, wherein the method comprises the following steps:
(1) stripping to obtain a waste nickel-cobalt-manganese ternary cathode material, and then oxidizing and roasting to obtain micron spherical waste NCM cathode active material particles;
(2) ball-milling the waste NCM positive electrode active material particles obtained in the step (1) in dilute acid A with the concentration of not higher than 0.5M at the rotating speed of 150-500 rpm, and then adding a surfactant to obtain a dispersion liquid dispersed with waste NCM ternary active material nanospheres;
(3) adding a carbon source into the nanosphere dispersion liquid obtained in the step (2), drying the nanosphere dispersion liquid after forming slurry, carbonizing the nanosphere dispersion liquid at the temperature of 800-1200 ℃, and etching the waste NCM active material nanosphere template in acid liquid B with the concentration not higher than 1M to obtain the nickel-cobalt-manganese polymetal @ graphitized carbon @ hierarchical porous carbon material.
5. The method of claim 4, wherein the spent NCM positive electrode active material has the formula LiNi0.5Co0.2Mn0.3O2、LiNi0.6CoMn0.2O2、LiNi0.8Co0.1Mn0.1O2、LiNi1/3Co1/3Mn1/3O2；
The temperature of oxidizing roasting is 300-900 ℃;
the particle size of the micron spherical waste NCM positive active material is 3-15 microns.
6. The method of claim 4, wherein the dilute acid A is at least one acid solution selected from hydrochloric acid, nitric acid and sulfuric acid;
preferably, the solid-to-liquid ratio of the acid solution to the waste NCM positive electrode active material particles is 0.1-10;
preferably, the ball milling time is 1-10 h;
preferably, the surfactant is one or more of CTAB, PVP, CTAB and SDS;
preferably, the concentration of the surfactant in the nanoparticle dispersion liquid is 0.1 to 1 wt%.
7. The method of claim 4, wherein the carbon source is one or more of sucrose, starch, polydopamine;
preferably, the acid solution B is one or more of sulfuric acid, hydrochloric acid and nitric acid, and the concentration is 0.05-0.5M;
preferably, the etching process is carried out under the condition of stirring for 1-10 hours at normal temperature.
8. A lithium-sulfur battery composite positive electrode active material, which is characterized by comprising the nickel-cobalt-manganese multi-metal @ graphitized carbon @ hierarchical porous carbon material according to any one of claims 1 to 3 or the nickel-cobalt-manganese multi-metal @ graphitized carbon @ hierarchical porous carbon material prepared by the preparation method according to any one of claims 4 to 7, and further comprising an elemental sulfur source;
preferably, the sulfur carrying amount of the composite positive electrode active material is 60-80 wt%.
9. A positive electrode material for a lithium-sulfur battery, comprising the composite positive electrode active material according to claim 8, further comprising a conductive agent and a binder;
preferably, the content of the conductive agent is 5-10 wt%; the content of the binder is 5-10 wt%.
10. A lithium sulfur battery, wherein a positive electrode of the lithium sulfur battery comprises the composite positive electrode active material according to claim 8;
preferably, the positive electrode material according to claim 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010048893.2A CN111180710B (en) | 2020-01-16 | 2020-01-16 | Nickel-cobalt-manganese multi-metal @ graphitized carbon @ hierarchical porous carbon material, preparation thereof and application thereof in lithium-sulfur battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010048893.2A CN111180710B (en) | 2020-01-16 | 2020-01-16 | Nickel-cobalt-manganese multi-metal @ graphitized carbon @ hierarchical porous carbon material, preparation thereof and application thereof in lithium-sulfur battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111180710A true CN111180710A (en) | 2020-05-19 |
| CN111180710B CN111180710B (en) | 2021-05-11 |
Family
ID=70649539
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010048893.2A Active CN111180710B (en) | 2020-01-16 | 2020-01-16 | Nickel-cobalt-manganese multi-metal @ graphitized carbon @ hierarchical porous carbon material, preparation thereof and application thereof in lithium-sulfur battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111180710B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112010358A (en) * | 2020-08-24 | 2020-12-01 | 蜂巢能源科技有限公司 | Carbon-doped ternary precursor, preparation method thereof, ternary cathode material and lithium ion battery |
| CN112820864A (en) * | 2020-12-31 | 2021-05-18 | 中国科学院苏州纳米技术与纳米仿生研究所 | Defect-based compound anchored single-atom composite material and preparation method and application thereof |
| CN114031125A (en) * | 2021-11-05 | 2022-02-11 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of ternary nanosheet @ carbon nanotube positive electrode material, product and application thereof |
| CN114956132A (en) * | 2021-12-21 | 2022-08-30 | 昆明理工大学 | Method for selectively extracting lithium and recycling waste lithium ion batteries |
| CN116371465A (en) * | 2023-01-19 | 2023-07-04 | 广东邦普循环科技有限公司 | Method for preparing photocatalytic material by using ternary precursor high-magnetic waste and application |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102130336A (en) * | 2011-02-12 | 2011-07-20 | 中南大学 | Hierarchical pore structure carbon cathode material for lithium iron battery and preparation method |
| WO2017091271A2 (en) * | 2015-09-03 | 2017-06-01 | Navitas Systems, Llc | Cathode and cathode materials for lithium sulfur batteries |
| CN108455562A (en) * | 2018-05-07 | 2018-08-28 | 中南大学 | A kind of thin wall type local graphitization porous carbon ball material and preparation method thereof and the application in lithium-sulfur cell |
| CN108666537A (en) * | 2017-03-31 | 2018-10-16 | 中南大学 | A kind of lithium-sulfur battery composite cathode material and preparation method thereof and lithium-sulfur cell application |
-
2020
- 2020-01-16 CN CN202010048893.2A patent/CN111180710B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102130336A (en) * | 2011-02-12 | 2011-07-20 | 中南大学 | Hierarchical pore structure carbon cathode material for lithium iron battery and preparation method |
| WO2017091271A2 (en) * | 2015-09-03 | 2017-06-01 | Navitas Systems, Llc | Cathode and cathode materials for lithium sulfur batteries |
| CN108666537A (en) * | 2017-03-31 | 2018-10-16 | 中南大学 | A kind of lithium-sulfur battery composite cathode material and preparation method thereof and lithium-sulfur cell application |
| CN108455562A (en) * | 2018-05-07 | 2018-08-28 | 中南大学 | A kind of thin wall type local graphitization porous carbon ball material and preparation method thereof and the application in lithium-sulfur cell |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112010358A (en) * | 2020-08-24 | 2020-12-01 | 蜂巢能源科技有限公司 | Carbon-doped ternary precursor, preparation method thereof, ternary cathode material and lithium ion battery |
| CN112820864A (en) * | 2020-12-31 | 2021-05-18 | 中国科学院苏州纳米技术与纳米仿生研究所 | Defect-based compound anchored single-atom composite material and preparation method and application thereof |
| CN114031125A (en) * | 2021-11-05 | 2022-02-11 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of ternary nanosheet @ carbon nanotube positive electrode material, product and application thereof |
| CN114031125B (en) * | 2021-11-05 | 2023-11-28 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of ternary nano sheet@carbon nano tube anode material, product and application thereof |
| CN114956132A (en) * | 2021-12-21 | 2022-08-30 | 昆明理工大学 | Method for selectively extracting lithium and recycling waste lithium ion batteries |
| CN114956132B (en) * | 2021-12-21 | 2023-10-20 | 昆明理工大学 | Method for selectively extracting lithium and recycling waste lithium ion batteries |
| CN116371465A (en) * | 2023-01-19 | 2023-07-04 | 广东邦普循环科技有限公司 | Method for preparing photocatalytic material by using ternary precursor high-magnetic waste and application |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111180710B (en) | 2021-05-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111180710B (en) | Nickel-cobalt-manganese multi-metal @ graphitized carbon @ hierarchical porous carbon material, preparation thereof and application thereof in lithium-sulfur battery | |
| Lavoie et al. | High gravimetric capacity and long cycle life in Mn3O4/graphene platelet/LiCMC composite lithium-ion battery anodes | |
| Chae et al. | A Li-ion battery using LiMn2O4 cathode and MnOx/C anode | |
| CN111193019A (en) | Lithium supplement additive, preparation method thereof and lithium ion battery | |
| CN110518228B (en) | Inorganic nanoparticle embedded three-dimensional grapheme carbon nanocomposite and application thereof | |
| Kim et al. | Remarkable improvement in cell safety for Li [Ni0. 5Co0. 2Mn0. 3] O2 coated with LiFePO4 | |
| CN107732203B (en) | Preparation method of nano cerium dioxide/graphene/sulfur composite material | |
| Gao et al. | Preparation and modification of MIL-101 (Cr) metal organic framework and its application in lithium-sulfur batteries | |
| Li et al. | Hollow graphene spheres coated separator as an efficient trap for soluble polysulfides in LiS battery | |
| CN111244445B (en) | Lithium-sulfur battery composite positive electrode active material and preparation and application thereof | |
| CN110957481A (en) | Porous silicon-carbon composite material and preparation method thereof | |
| US20190267615A1 (en) | Oxyfluoride cathodes and a method of producing the same | |
| Jiang et al. | A sustainable strategy for spent Li-ion battery regeneration: microwave-hydrothermal relithiation complemented with anode-revived graphene to construct a LiFePO 4/MWrGO cathode material | |
| CN113113681A (en) | Composite sodium supplement additive and application thereof in sodium ion battery | |
| CN115588734A (en) | Composite lithium supplement agent and preparation method thereof | |
| Guo et al. | Si/SnSb alloy composite as high capacity anode materials for Li-ion batteries | |
| Li et al. | N, S-doped graphene derived from graphene oxide and thiourea-formaldehyde resin for high stability lithium–sulfur batteries | |
| CN102290576A (en) | Multi-doped lithium phosphate anode material, preparation method and lithium ion power cell thereof | |
| Andreas Arie et al. | Potato Peel Based Carbon–Sulfur Composite as Cathode Materials for Lithium Sulfur Battery | |
| CN110600710B (en) | Iron sulfide-carbon composite material and preparation method thereof, lithium ion battery negative electrode material, lithium ion battery negative electrode piece and lithium ion battery | |
| CN112768679A (en) | One-dimensional pea-shaped bimetallic ferric vanadate nanowire material and preparation method and application thereof | |
| CN115483371A (en) | Lithium-rich porous graphite material and preparation method and application thereof | |
| Gan et al. | Continuous Flow Electrochemical Synthesis of Olivine‐Structured NaFePO4 Cathode Material for Sodium‐Ion Batteries from Recycle LiFePO4 | |
| CN106058247B (en) | Monodisperse lithium iron phosphate nanometer rods and its preparation method and application | |
| CN113285066B (en) | Vanadium phosphate @ carbon/expanded microcrystalline graphite composite negative electrode active material for potassium ion battery and preparation and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |