CN111916686B - Phosphorus-containing lithium ion battery cathode material and preparation process thereof - Google Patents

Phosphorus-containing lithium ion battery cathode material and preparation process thereof Download PDF

Info

Publication number
CN111916686B
CN111916686B CN201910378696.4A CN201910378696A CN111916686B CN 111916686 B CN111916686 B CN 111916686B CN 201910378696 A CN201910378696 A CN 201910378696A CN 111916686 B CN111916686 B CN 111916686B
Authority
CN
China
Prior art keywords
phosphorus
negative electrode
electrode material
lithium ion
ion battery
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.)
Active
Application number
CN201910378696.4A
Other languages
Chinese (zh)
Other versions
CN111916686A (en
Inventor
孙赛
高焕新
刘志成
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
Original Assignee
China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by China Petroleum and Chemical Corp, Sinopec Shanghai Research Institute of Petrochemical Technology filed Critical China Petroleum and Chemical Corp
Priority to CN201910378696.4A priority Critical patent/CN111916686B/en
Publication of CN111916686A publication Critical patent/CN111916686A/en
Application granted granted Critical
Publication of CN111916686B publication Critical patent/CN111916686B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

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
    • 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
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • H01M4/36—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
    • H01M4/386—Silicon or alloys based on silicon
    • 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
    • H01M4/387—Tin or alloys based on tin
    • 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
    • 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
    • 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 discloses a phosphorus-containing lithium ion battery cathode material, a preparation process and a lithium ion battery based on the cathode material. The phosphorus-containing lithium ion battery cathode material comprises phosphorus element, active components and carbon nanofibers, has the characteristics of high specific capacity, high cycle reversibility, excellent rate performance and the like, and is suitable for preparing a power type lithium ion battery with high energy density.

Description

Phosphorus-containing lithium ion battery cathode material and preparation process thereof
Technical Field
The invention relates to a phosphorus-containing lithium ion battery cathode material and a preparation process thereof.
Background
Lithium batteries can be divided into consumer lithium ion batteries, power lithium ion batteries, and energy storage lithium ion batteries according to downstream applications. With the rapid development of new energy fields in recent years, the market demand for high energy density lithium batteries is increasing. In 2017, the ministry of industry and informatization and the like jointly printed a scheme for promoting the development action of the automobile power battery industry. In the scheme, the specific energy of the novel lithium ion power battery cell exceeds 300Wh/Kg by 2020. However, the current commercialized lithium ion battery cathode material is mainly a carbon material, the theoretical specific capacity is only 372mAh/g, and the future requirement on a high-energy density lithium battery cannot be realized at all. Therefore, the development of new anode materials has become a focus of current interest.
The non-carbon negative electrode material has higher theoretical specific capacity (Si:4200 mA.h.g) -1 、Sn:994mA·h·g -1 、Ge:1600mA·h·g -1 ) The method becomes a research hotspot of novel cathode materials, and provides eosin for realizing the stable improvement of the capacity density of the lithium battery. However, the materials of the class generally cause large volume expansion (150% -400%) during deep charging and discharging, so that electrode pulverization failure is caused, and finally, the problems of battery short circuit, performance attenuation and the like are caused. In order to solve the above problems, the prior art generally improves the performance by means of composite and coating. For example, the authorization number is CN103367727B, Chinese patent application, discloses a nanometer silicon-carbon composite cathode material. By coating the organic cracking carbon on the surface of the nano silicon/graphite polymer, the volume expansion of the silicon nano particles is relieved, the phenomenon of breaking the silicon particles is avoided, and the performance of the cathode material is improved. For another example, chinese patent No. CN102903896A discloses a silicon-carbon composite negative electrode material for a lithium ion battery and a preparation method thereof, where the negative electrode material is of a core-shell structure. The nano silicon is used as a core body, the amorphous carbon is used as a buffer layer, the one-dimensional nano carbon material shell is coated on the outer layer by utilizing a spray pyrolysis method, and the carbon on the middle layer and the outermost layer can buffer the volume expansion of the silicon material to the maximum extent, so that the performance deterioration of the negative electrode material caused by the volume expansion of the silicon is greatly reduced. Although the invention can relieve the performance deterioration caused by the volume expansion of the non-carbon negative electrode material, the content of active components in the system is low (less than or equal to 10 percent), and the improvement on the specific capacity of the material is limited. When the content of the active component is further increased (more than or equal to 15%), the problems of binder failure, electrode corrosion, battery short circuit and the like caused by volume effect are more obvious, and the existing process can not be effectively solved. In 2012, chinese patent with the authorization number CN101527357B discloses a nano-silicon amorphous carbon composite lithium ion battery anode material and a preparation method thereof, wherein a nano-silicon @ carbon core-shell structure is prepared by an electrostatic spinning method. The method obviously improves the content of silicon (10-50%) in the material, but the adoption of a single-shaft electrostatic spinning process is difficult to completely coat the amorphous carbon layer with silicon nanoparticles, the first coulomb efficiency of the material is low, and the cycle performance is not ideal. Subsequently, chinese patent with application publication No. CN106571451A discloses a silicon carbon negative electrode material prepared by a coaxial electrospinning process. The core-shell structure of the material is kept complete, the coulombic efficiency is obviously improved, and the cycle life is long. But the coaxial electrostatic process is complex, the spinning process is difficult to control, the industrialization cost is high, and the large-scale popularization is not facilitated.
Therefore, the development of the cathode material with high electroactive substance content, excellent electrochemical performance, excellent stability, simple and controllable preparation process and easy large-scale production belongs to the technical problem in the field.
Disclosure of Invention
The invention aims to provide a phosphorus-containing lithium ion battery negative electrode material.
A phosphorus-containing lithium ion battery cathode material comprises a phosphorus element, an active component and carbon nanofibers.
In the technical scheme, the phosphorus element in the negative electrode material is connected with the active component through a chemical bond.
In the technical scheme, the phosphorus element in the negative electrode material is connected with the carbon nanofibers through chemical bonds.
In the above technical solution, the negative electrode material includes a p (O) -O-R structural segment, and R includes any one of carbon, silicon, phosphorus, germanium, tin, vanadium, and titanium.
In the technical scheme, the cathode material has a core-shell structure, the core comprises an active component, and the shell comprises a phosphorus element; the active component is loaded on the outside or/and the inside of the nano carbon fiber.
In the above technical solution, the active component in the negative electrode material includes any one or more of silicon, germanium, tin, vanadium, and titanium.
In the technical scheme, the mass parts of the phosphorus element in the negative electrode material are 0.1-12 parts and the mass parts of the active component are 5-90 parts.
In the technical scheme, the diameter of the carbon nanofiber in the negative electrode material is 50 nm-1 mu m; the specific surface area of the negative electrode material is preferably 1m 2 /g～1000m 2 A/g of preferably 25m 2 /g～300m 2 /g。
The invention also provides a preparation process of the phosphorus-containing lithium ion battery cathode material, which comprises the following steps: and (3) carrying out electrostatic spinning and heat treatment on the spinning solution containing the organic carbon source, the phosphorus source and the active component.
In the above technical scheme, the organic carbon source in the preparation process comprises any one or more of cellulose acetate, chitosan, polyacrylic acid, polyvinylpyrrolidone, hydroxypropyl cellulose, polyester polyurethane, homopolyacrylonitrile, copolymeric polyacrylonitrile, polyvinyl acetate, polyimide, polyamide, and modified asphalt.
In the above technical solution, the phosphorus source in the preparation process includes a compound containing a phosphoric acid group, preferably the phosphorus source includes any one or more of phytic acid, phosphoric acid, metaphosphoric acid, and polyphosphoric acid; the active component in the cathode material comprises one or more of silicon, germanium, tin, vanadium and titanium; preferably, the mass ratio of the phosphorus source to the active component in the preparation process is 1: 0.9-1: 36.
In the technical scheme, the technological parameters of electrostatic spinning in the preparation technology are positive voltage of 5 KV-30 KV and/or negative voltage of-0.2 KV-10 KV, and/or the distance between a spinning opening and a receiver is 5 cm-30 cm, and/or the injection speed of the spinning solution is 0.02mm/min-0.8 mm/min.
In the technical scheme, the heat treatment in the preparation process comprises a roasting step at 200-1200 ℃, and preferably, the heat treatment comprises a heat treatment step at 200-450 ℃ and a heat treatment step at 500-1200 ℃. The present invention also includes a lithium ion battery comprising:
the phosphorus-containing lithium ion battery cathode material is used as a cathode;
a positive electrode material containing lithium element, a separator, and an electrolyte.
In the above technical solution, the lithium ion battery includes any one of a liquid lithium ion battery, a semi-solid lithium ion battery, or an all-solid lithium ion battery.
Technical effects
The cathode material of the invention contains phosphorus element, and can solve the problem that the electroactive material is difficult to disperse in the solvent.
According to the cathode material, the phosphorus-containing buffer layer coated on the surface of the electroactive material avoids the problems of electrode material pulverization, uncontrollable SEI film growth and the like caused by volume effect of the electroactive material in the charging and discharging processes.
According to the cathode material disclosed by the invention, the electroactive substance and the carbon nanofibers are connected together through the phosphorus-containing buffer layer, so that the stability of the electroactive substance in the carbon nanofibers is improved, and the cathode material has a remarkable effect of improving the cycle stability of the cathode material.
According to the preparation method of the anode material, the phosphoric acid functional group contained in the phosphorus source can promote the ring formation reaction in the pre-oxidation stage of the polymer fiber (as shown in figure 1), and is favorable for forming the self-supporting anode material with excellent thermal stability and mechanical property.
The phosphorus-containing lithium battery negative electrode material provided by the invention does not need to add a conductive agent and a bonding agent in the using process, greatly reduces the quality and cost of the lithium battery, and can obviously improve the energy density of the lithium battery.
Drawings
FIG. 1 is a diagram showing the mechanism of the phosphorus-containing group promoting the polyacrylonitrile ring formation reaction.
FIG. 2 is a TEM image of the phosphorus-containing buffer layer coated with nano-silicon, where A is the nano-silicon particles and B is the phosphorus-containing buffer layer.
Fig. 3 is a TEM photograph of the anode material described in example 1.
Fig. 4 is a schematic structural diagram of the negative electrode material in example 1, where a is carbon nanofibers, B is a phosphorus-containing buffer layer, and C is nano silicon particles.
FIG. 5 is an X-ray photoelectron spectrum of C1s of the negative electrode material for the phosphorus-containing lithium battery of example 1.
FIG. 6 is an X-ray photoelectron spectrum of P2P of the negative electrode material for phosphorus-containing lithium battery of example 1.
FIG. 7 is an X-ray photoelectron spectrum of Si2p of the negative electrode material for phosphorus-containing lithium battery of example 1.
FIG. 8 is a first charge and discharge curve of the negative electrode material for a phosphorus-containing lithium battery of example 1.
FIG. 9 is a cycle stability test curve of the negative electrode material for a phosphorus-containing lithium battery in example 1.
FIG. 10 is an X-ray photoelectron spectrum of C1s of the negative electrode material for a lithium battery in the comparative example.
FIG. 11 is an X-ray photoelectron spectrum of Si2p of the negative electrode material for a lithium battery in the comparative example.
Fig. 12 is a cycle stability test curve of the negative electrode material for a lithium battery in the comparative example.
Detailed Description
In order to facilitate understanding of the present invention, the present invention will be described below by way of examples. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention. The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values.
All publications, patent applications, patents, and other references mentioned in this specification are herein incorporated by reference in their entirety. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. In case of conflict, the present specification, including definitions, will control.
In the context of this specification, any two or more aspects of the present invention may be combined in any combination, and the resulting solution is part of the original disclosure of this specification, and is intended to be within the scope of the present invention.
In the context of the present specification, the specific surface area refers to the total area per unit mass of the negative electrode material, including the outer surface area and the inner surface area.
Where not explicitly stated, all percentages, parts, ratios, etc. referred to in this specification are by weight unless otherwise not in accordance with routine knowledge of those skilled in the art.
The present invention relates to the following embodiments.
According to one aspect of the invention, the invention relates to a phosphorus-containing lithium ion battery anode material which comprises phosphorus, an active component and carbon nanofibers.
According to one aspect of the invention, the active component refers to an electroactive species. Preferably comprising any one or more of elemental components comprising silicon, germanium, tin, vanadium, titanium, such as silicon, silicon-germanium, silicon-tin, and the like.
According to an aspect of the present invention, the phosphorus element in the anode material is connected to the active component by a chemical bond. Preferably P (O) -O-R 1 Wherein R is 1 Is an active component. By chemical bond is meant the formation of covalent bonds between the phosphorus-containing component and the active component, for example, the phosphorus-containing component is bonded to the active component by P (O) -O-Si (covalent bond), P (O) -O-Sn (covalent bond), P (O) -O-Ti, and the like.
According to one aspect of the invention, the phosphorus element in the negative electrode material is connected with the carbon nanofibers through chemical bonds. Preferably, the phosphorus-containing component is attached to the filamentous nanocarbon via a-C (O) -O-P- (covalent bond).
According to one aspect of the invention, the negative electrode material comprises a P (O) -O-R structural segment, namely the negative electrode material comprises a component containing the P (O) -O-R structural segment, and R comprises any one element of carbon, silicon, phosphorus, germanium, tin, vanadium and titanium elements. This was obtained by XPS characterization.
According to one aspect of the invention, the anode material has a core-shell structure, the core has an active component therein, and the shell has a phosphorus element therein; the phosphorus-containing component is coated on the surface of the active material to form a phosphorus-containing buffer layer, as shown in fig. 2, so that a core-shell structure is formed. The active component is loaded on the outer surface or the inner surface of the carbon nanofiber, and the active component is connected with the carbon nanofiber through a phosphorus-containing buffer layer. This was observed by electron microscopy.
According to one aspect of the invention, the mass fraction of the phosphorus element in the negative electrode material is 0.1-12 parts, such as 0.12 part, 0.2 part, 1 part, 3 parts, 5 parts and 12 parts, based on the mass fraction of the negative electrode material. The active component is 5-90 parts by mass, such as 5 parts, 10 parts, 30 parts, 60 parts, 90 parts and the like.
According to one aspect of the present invention, the term "filamentous nanocarbon" refers to a carbon material having a diameter of a nanometer scale formed by carbonizing a high molecular polymer such as polyacrylonitrile or the like at a high temperature, and preferably the filamentous nanocarbon has a diameter of 50nm to 1 μm, more preferably 100nm to 900nm, for example, 100nm, 200nm, 300nm, 400nm, 500nm, 700nm, 900nm or the like. The diameter refers to an average diameter of the carbon nanofibers, which is observed by a scanning electron microscope.
According to an aspect of the present invention, the filamentous nanocarbon contains a functional group, which is a heteroatom-containing functional group, including C N, C-N, C O, C (O) -O, etc.
According to an aspect of the present invention, the anode material has a specific surface area of 1m 2 /g～1000m 2 Per g, more preferably 25m 2 /g～300m 2 G, e.g. 30m 2 /g、40m 2 /g、45m 2 /g、55m 2 /g、70m 2 /g、100m 2 /g、125m 2 /g、150m 2 /g、200m 2 /g、250m 2 And/g, etc. The specific surface area is obtained by a BET method test.
According to one aspect of the invention, the preparation process of the phosphorus-containing lithium ion battery negative electrode material comprises the following steps: and (3) carrying out electrostatic spinning on the spinning solution containing the organic carbon source, the phosphorus source and the active component, and then carrying out heat treatment.
According to one aspect of the invention, the preparation process comprises the following steps: 1) contacting a phosphorus source with an active component; 2) and (3) carrying out electrostatic spinning and heat treatment on the spinning solution containing the organic carbon source, the phosphorus source and the active component.
According to one aspect of the invention, contacting the phosphorus source with the active component is specifically achieved by contacting the phosphorus source with the active component for sonication to form a phosphorus-coated active component. The phosphorus source and the active component are preferably sonicated in a solvent. The solvent may be a solvent commonly used in laboratories, such as N 'N-dimethylformamide, N' N-dimethylacetamide, N-methylpyrrolidone, water, and the like.
According to an aspect of the present invention, the spinning solution containing the organic carbon source, the phosphorus source and the active component can be prepared by a method conventionally used for this purpose in the art, such as preparing the organic carbon source, the phosphorus source, the active component and a solvent into a spinning solution containing the high molecular polymer and the active component. The ratio of the organic carbon source to the active component to the solvent is 1-2: 15-20.
According to one aspect of the invention, the organic carbon source in the preparation process comprises one or more of cellulose acetate, chitosan, polyacrylic acid, polyvinylpyrrolidone, hydroxypropyl cellulose, polyester polyurethane, polyacrylonitrile copolymer, polyvinyl acetate, polyimide, polyamide and modified asphalt, and further preferably comprises one or more of polyacrylonitrile, polyacrylonitrile copolymer, polyvinylpyrrolidone and polyimide.
According to one aspect of the invention, the active component comprises any one or more of the components containing the elements silicon, germanium, tin, vanadium, titanium, such as silicon, silicon-germanium, silicon-tin, tin-titanium, silicon-titanium, and the like.
According to one aspect of the invention, the phosphorus source comprises a compound comprising a phosphorus acid group. Preferably, the phosphorus source comprises any one or more of phytic acid, phosphoric acid, metaphosphoric acid and polyphosphoric acid. Particularly, any one of phytic acid and phosphoric acid is preferable. As shown in fig. 2, the phosphorus source is coated on the surface of the electroactive material by a solution method to form a core-shell structure.
According to one aspect of the invention, the mass ratio of the phosphorus source to the active component in the preparation process is 1: 0.9-1: 36, such as 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:10, 1:12, etc., and more preferably 1: 3-1: 12, such as 1:3, 1:6, 1:12, etc.
According to one aspect of the invention, the electrostatic spinning process parameter in the preparation process is forward voltage 5 KV-30 KV, for example, 8KV, 11KV, 12KV, 15KV, 20KV, 22KV and the like; negative voltage is-0.2 KV-10 KV, such as-1 KV, -1.5KV, -2KV, -3KV, -5KV, -8KV, etc.; the distance between the spinning opening and the receiver is 5 cm-30 cm, for example, 5cm, 8cm, 12cm, 15cm, 17.5cm and the like; the injection speed of the spinning solution is 0.02mm/min to 0.8mm/min, for example, 0.08mm/min, 0.1mm/min, 0.2mm/min, 0.3mm/min, 0.5mm/min, etc.
According to one aspect of the present invention, the heat treatment may be performed in any manner conventionally known in the art, such as a heat treatment comprising two steps of a low temperature heat treatment at 200 ℃ to 1200 ℃ and a high temperature heat treatment, preferably comprising two steps of a low temperature heat treatment at 200 ℃ to 450 ℃ and a high temperature heat treatment at 500 ℃ to 1200 ℃, further preferably 200 ℃ to 300 ℃, for example 200 ℃, 250 ℃, 260 ℃, 290 ℃, 300 ℃ and the like, and further preferably 650 ℃ to 900 ℃, for example 650 ℃, 700 ℃, 750 ℃, 800 ℃, 900 ℃ and the like. The high temperature heat treatment is generally carried out under an inert-containing atmosphere, such as a nitrogen or argon atmosphere. The high-temperature roasting temperature range of the precursor in the preparation process is 500-1200 ℃, for example, 500 ℃, 600 ℃, 750 ℃, 800 ℃, 1100 ℃, 1200 ℃ and the like. The heating rate of the heat treatment is 1 ℃/min to 10 ℃/min, for example, 1 ℃/min, 5 ℃/min, 10 ℃/min.
According to one aspect of the invention, the preparation process is carried out by oiling or drawing before the heat treatment. The oiling may be carried out in any manner conventionally known in the art, such as: before the heat treatment, the resultant was immersed in polyether silicone oil, dried, and then placed in an atmosphere furnace to be heat-treated. The draw treatment may be carried out in any manner conventionally known in the art, for example: the sample was placed in a stainless steel furnace tube and drawn at a rate of 3cm/min under saturated steam pressure with a draw ratio of 2.5 and a setting time of 5 minutes. And after finishing, naturally cooling to room temperature.
According to one aspect of the invention, the lithium ion battery comprises the phosphorus-containing lithium ion battery anode material, a lithium element-containing cathode material, a separator and an electrolyte.
According to one aspect of the invention, the negative electrode plate of the lithium ion battery does not contain any one or more of a conductive agent, an adhesive and a metal current collector.
According to an aspect of the present invention, the lithium ion battery includes any one of a liquid lithium ion battery, a semi-solid lithium ion battery, or an all-solid lithium ion battery.
In the context of the present specification, including the following examples and comparative examples, a scanning electron microscope model of TECNALG2F20(200kv) from FEI company, usa was used. And (3) testing conditions: the sample was pressed directly onto the sample stage containing the conductive tape and then observed by insertion into an electron microscope. The observation was performed using a magnification of 1 ten thousand. Observing the nanofibers under the magnification of 1 ten thousand times, randomly selecting an observation visual field, and calculating the average value of the effective diameters of all the nanofibers in the observation visual field. The operation was repeated a total of 10 times. The effective diameter is defined as the average of the sum of the 10-fold averages.
In the context of the present specification, including the following examples and comparative examples, a JEM-2100 transmission electron microscope of Japan Electron Co., Ltd is used. And (3) testing conditions are as follows: the accelerating voltage is 160KV, and the sample is placed in a copper support net and then inserted into an electron microscope for observation. The observation was carried out using 80 ten thousand times of magnification.
In the context of the present description, including the examples and comparative examples below, an X-ray photoelectron spectroscopy tester of the model ESCALB 250Xi from ThermoFisher Scientific, USA, is used. And (3) testing conditions are as follows: room temperature 25 deg.C, vacuum degree less than 5 × 10 -10 mba, working voltage 15KV, using Al K alpha as ray source.
In the context of the present description, including the examples and comparative examples below, a thermal integrated analyzer model SDT Q600 from the company tas instruments, usa was used. And (3) testing conditions are as follows: the testing interval is 25-800 ℃, the gas flow rate is 100ml/min, and the temperature rise rate is 10 ℃/min.
In the context of the present specification, including in the examples and comparative examples below, the american Micromeritics company ASAP2010 specific surface area and pore size distribution determinator was employed. And (3) testing conditions are as follows: temperature 77K, nitrogen atmosphere.
In the context of the present specification, including the examples and comparative examples below, the wuhan blue battery test system (CT2001B) was employed. And (3) testing conditions are as follows: the voltage range is 0.005V-3V, and the current range is 0.05A-2A. 10 coin cells were assembled per sample and cell performance was tested at the same voltage and current. In the context of the present specification, the following examples and comparative examples are included, and therefore, the drugs and raw materials may be either commercially available or may be manufactured according to the knowledge of the prior art.
Example 1
1) Get D 50 0.45g of 120nm silica powder was added to 8.65g of N 'N-dimethylformamide/phytic acid mixed solution (8.425g of N' N-dimethylformamide and 0.225g of phytic acid), and stirred for 40 minutes.
2) 0.9g of polyacrylonitrile copolymer (Mw 180000) was weighed and added to the solution in step 1, and stirred at 50 ℃ until all the polymer was dissolved, to obtain a spinning solution.
3) And transferring the spinning solution into a 10ml needle cylinder, and collecting a precursor of the phosphorus-containing negative electrode material under the conditions that the positive voltage is 12.2KV, the negative voltage is-2.0 KV, the distance between a spinning opening and a receiver is 15cm, and the injection speed of the spinning solution is 0.3 mm/min.
4) And (4) placing the precursor of the phosphorus-containing negative electrode material obtained in the step (3) in a tubular furnace, heating to 270 ℃ at the speed of 5 ℃/min, and preserving heat for 30 minutes in a nitrogen atmosphere. And then, heating to 800 ℃ at the speed of 10 ℃/min, preserving the heat for 15 minutes in the nitrogen atmosphere, and naturally cooling to room temperature after the heat preservation is finished to obtain the phosphorus-containing lithium battery cathode material. The negative electrode material has good mechanical property, can be folded, stretched and bent at will, exerts 5000N tensile force on the phosphorus-containing negative electrode material with the thickness of 1 mu m, and does not break. FIG. 2 is a TEM image of the phosphorus buffer layer coated with nano-silicon. It can be seen from the figure that the nano silicon particles are uniformly wrapped. Fig. 3 is a TEM photograph of a single nanofiber in the phosphorus-containing anode material. As can be seen from the figure, the silicon nanoparticles wrapped by the phosphorus buffer layer are distributed inside and outside the nanofibers. Accordingly, the negative electrode material is assumed to have a structure as shown in fig. 4.
FIG. 5 is an X-ray photoelectron spectrum of C1s of the negative electrode material for phosphorus-containing lithium battery of example 1. The presence of the C-O-P functional group can be confirmed from the figure, indicating that the nanofibrous carbon and the phosphorus containing buffer layer are linked by a C-O-P bond. FIG. 6 is an X-ray photoelectron spectrum of P2P of the negative electrode material for phosphorus-containing lithium battery of example 1. In this diagram, both P (O) -O-C functional groups and P (O) -O-Si functional groups are present. FIG. 7 is an X-ray photoelectron spectrum of Si2P of the negative electrode material for phosphorus-containing lithium battery of example 1, from which the presence of Si-O-P functional group can be confirmed. The three spectrogram results show that the nanometer silicon powder (electroactive substance) is connected with the nanometer carbon fiber through phytic acid (a phosphorus-containing buffer layer). The structure can not only ensure the stable existence of the nano silicon powder in the cathode material, but also buffer the performance attenuation caused by the silicon volume effect in the charging and discharging process. By usingBy thermogravimetric analysis, we determined that the content of silicon in the negative electrode material of phosphorus-containing lithium battery described in example 1 was 32%. The diameter was 340 nm. The specific surface area of the material is 118m measured by a BET method 2 /g。
The material described in example 1 and a metal lithium sheet were used as a positive electrode and a negative electrode, respectively, a 1mol/LLIPF6 solution was used as an electrolyte, a polypropylene microporous membrane was used as a separator, and the material was assembled into a CR2016 coin cell, which was used to characterize the electrical properties of the material described in example.
FIG. 8 shows the first charge-discharge curve (test voltage range 0.05-3V, current 50mA) of a button cell based on the material of example 1. As shown, the material described in example 1 had a reversible charge capacity of 1190mAh g -1 The first coulombic efficiency was 88.6%.
Fig. 9 shows the cycling stability test curve for coin cells based on the material described in example 1. As shown in the figure, the capacity retention rate of the material described in example 1 is greater than 95% after 100 cycles at a constant current discharge rate of 0.5C.
Example 2
1) Get D 50 0.45g of 50nm silica powder was added to 8.65g of N 'N-dimethylformamide/phytic acid mixed solution (8.425g of N' N-dimethylformamide and 0.225g of phytic acid), and stirred for 40 minutes.
2) 0.9g of polyacrylonitrile copolymer (Mw 180000) was weighed and added to the solution in step 1, and stirred at 50 ℃ until all the polymer was dissolved, to obtain a spinning solution.
3) And transferring the spinning solution into a 10ml needle cylinder, and collecting a precursor of the phosphorus-containing negative electrode material under the conditions that the positive voltage is 11.5KV, the negative voltage is-1.5 KV, the distance between a spinning opening and a receiver is 15cm, and the injection speed of the spinning solution is 0.3 mm/min.
4) And (4) placing the precursor of the phosphorus-containing negative electrode material obtained in the step (3) in a tubular furnace, heating to 270 ℃ at the speed of 5 ℃/min, and preserving heat for 30 minutes in a nitrogen atmosphere. And then, heating to 800 ℃ at the speed of 10 ℃/min, preserving the heat for 15 minutes in the nitrogen atmosphere, and naturally cooling to room temperature after the heat preservation is finished to obtain the phosphorus-containing lithium battery cathode material.
The materials described in example 2 were each usedThe metal lithium sheets are used as a positive electrode and a negative electrode, 1mol/LLIPF6 solution is used as electrolyte, a polypropylene microporous membrane is used as a diaphragm, and the CR2016 button cell is assembled, so that the electrical properties of the material in the embodiment are represented. The test results show that the material described in example 2 has a reversible charge capacity of 950mAh g -1 The initial coulombic efficiency is 82%, and the capacity retention rate of the material is more than 92% after 100 cycles under the constant-current discharge rate of 0.5C.
Example 3
1) Get D 50 0.45g of 50nm silica powder was added to 8.65g of N 'N-dimethylformamide/phytic acid mixed solution (8.425g of N' N-dimethylformamide and 0.225g of phytic acid), and stirred for 40 minutes.
2) 0.9g of polyvinylpyrrolidone (Mw. 1300000) was weighed and added to the solution in step 1, and stirred at 50 ℃ until all the polymer was dissolved, to obtain a spinning solution.
3) And transferring the spinning solution into a 10ml needle cylinder, and collecting a precursor of the phosphorus-containing negative electrode material under the conditions that the positive voltage is 14KV, the negative voltage is-2.3 KV, the distance between a spinning opening and a receiver is 15cm, and the injection speed of the spinning solution is 0.2 mm/min.
4) And (4) placing the precursor of the phosphorus-containing negative electrode material obtained in the step (3) in a tubular furnace, heating to 600 ℃ at the speed of 5 ℃/min, preserving the heat for 15 minutes in a nitrogen atmosphere, and naturally cooling to room temperature after the heat preservation, thus obtaining the phosphorus-containing lithium battery negative electrode material.
The material described in example 3 and a metal lithium sheet were used as a positive electrode and a negative electrode, respectively, a 1mol/LLIPF6 solution was used as an electrolyte, a polypropylene microporous membrane was used as a separator, and the material was assembled into a CR2016 coin cell, which was used to characterize the electrical properties of the material described in example. The test results show that the reversible charge capacity of the material described in example 3 is 1080mAh g -1 The initial coulombic efficiency is 83%, and the capacity retention rate of the material is more than 91% after 60 cycles under the constant current discharge rate of 0.5C.
Example 4
1) Get D 50 0.45g of 50nm silicon powder was added to 8.35g of an N 'N-dimethylformamide/phosphoric acid mixed solution (8.125g of N' N-dimethylformamide and 0.225g of phosphoric acid), and stirredStirring for 40 minutes.
2) 1.2g of polyimide (Mw 98000) was weighed and added to the solution in step 1, and stirred at 60 ℃ until all the polymer was dissolved, to obtain a spinning solution.
3) And transferring the spinning solution into a 10ml needle cylinder, and collecting a precursor of the phosphorus-containing negative electrode material under the conditions that the positive voltage is 14.5KV, the negative voltage is-3 KV, the distance between a spinning opening and a receiver is 15cm, and the injection speed of the spinning solution is 0.2 mm/min.
4) And (4) placing the precursor of the phosphorus-containing negative electrode material obtained in the step (3) in a tubular furnace, heating to 900 ℃ at the speed of 5 ℃/min, preserving the heat for 60 minutes in a nitrogen atmosphere, and naturally cooling to room temperature after the heat preservation, thus obtaining the phosphorus-containing lithium battery negative electrode material.
The material described in example 4 and a metal lithium sheet were used as a positive electrode and a negative electrode, respectively, a 1mol/LLIPF6 solution was used as an electrolyte, a polypropylene microporous membrane was used as a separator, and the material was assembled into a CR2016 coin cell, which was used to characterize the electrical properties of the material described in example. The test results show that the material described in example 4 has a reversible charge capacity of 1250mAh g -1 The initial coulombic efficiency is 84%, and the capacity retention rate of the material is more than 93% after 150 cycles under the constant current discharge rate of 0.5C.
Example 5
1) Get D 50 0.45g of 120nm silicon powder was added to 8.65g of an N 'N-dimethylformamide/phosphoric acid mixed solution (8.425g of N' N-dimethylformamide and 0.225g of phosphoric acid), and stirred for 40 minutes.
2) 0.9g of homopolyacrylonitrile (Mw 150000) was weighed and added to the solution in step 1, and stirred at 50 ℃ until all the polymer was dissolved, to obtain a spinning solution.
3) And transferring the spinning solution into a 10ml needle cylinder, and collecting a precursor of the phosphorus-containing negative electrode material under the conditions that the positive voltage is 12.2KV, the negative voltage is-1.5 KV, the distance between a spinning opening and a receiver is 15cm, and the injection speed of the spinning solution is 0.3 mm/min.
4) And (4) placing the precursor of the phosphorus-containing negative electrode material obtained in the step (3) in a tubular furnace, heating to 270 ℃ at the speed of 5 ℃/min, and preserving heat for 30 minutes in a nitrogen atmosphere. And then, heating to 800 ℃ at the speed of 10 ℃/min, preserving the heat for 15 minutes in the nitrogen atmosphere, and naturally cooling to room temperature after the heat preservation is finished to obtain the phosphorus-containing lithium battery cathode material.
The material described in example 5 and a metal lithium sheet were used as a positive electrode and a negative electrode, a 1mol/LLIPF6 solution was used as an electrolyte, a polypropylene microporous membrane was used as a separator, and a CR2016 coin cell was assembled. The test results show that the material described in example 5 has a reversible charge capacity of 1120mAh g -1 The initial coulombic efficiency is 81%, and the capacity retention rate of the material is more than 90% after 50 cycles under the constant current discharge rate of 0.5C.
Example 6
1) 0.45g of tin dioxide was added to 8.65g of an N 'N-dimethylformamide/phytic acid mixed solution (8.425g of N' N-dimethylformamide and 0.225g of phytic acid), and stirred for 40 minutes.
2) 0.9g of homopolyacrylonitrile (Mw 150000) was weighed and added to the solution in step 1, and stirred at 50 ℃ until all the polymer was dissolved, to obtain a spinning solution.
3) And transferring the spinning solution into a 10ml needle cylinder, and collecting a precursor of the phosphorus-containing negative electrode material under the conditions that the positive voltage is 8KV, the negative voltage is-1 KV, the distance between a spinning opening and a receiver is 15cm, and the injection speed of the spinning solution is 0.3 mm/min.
4) And (4) placing the precursor of the phosphorus-containing negative electrode material obtained in the step (3) into a tube furnace, heating to 200 ℃ at the speed of 5 ℃/min, and preserving heat for 30 minutes in a nitrogen atmosphere. And then, heating to 800 ℃ at the speed of 10 ℃/min, preserving the heat for 15 minutes in the nitrogen atmosphere, and naturally cooling to room temperature after the heat preservation is finished to obtain the phosphorus-containing lithium battery cathode material.
The material described in example 6 and a metal lithium sheet were used as a positive electrode and a negative electrode, respectively, a 1mol/LLIPF6 solution was used as an electrolyte, a polypropylene microporous membrane was used as a separator, and the material was assembled into a CR2016 coin cell, which was used to characterize the electrical properties of the material described in example. The test results show that the material described in example 6 has a reversible charge capacity of 420mAh g -1 The first coulombic efficiency is 86.7 percent, after the material is circulated for 200 times under the constant current discharge rate of 0.5C,the capacity retention rate is more than 95%.
Example 7
1) 0.45g of tin powder was added to 8.65g of a N 'N-dimethylformamide/phytic acid mixed solution (8.425g of N' N-dimethylformamide and 0.225g of phytic acid), and stirred for 40 minutes.
2) 0.9g of homopolyacrylonitrile (Mw 150000) was weighed and added to the solution in step 1, and stirred at 50 ℃ until all the polymer was dissolved, to obtain a spinning solution.
3) And transferring the spinning solution into a 10ml needle cylinder, and collecting a precursor of the phosphorus-containing negative electrode material under the conditions that the positive voltage is 10KV, the negative voltage is-1.5 KV, the distance between a spinning opening and a receiver is 15cm, and the injection speed of the spinning solution is 0.2 mm/min.
4) And (4) placing the precursor of the phosphorus-containing negative electrode material obtained in the step (3) into a tube furnace, heating to 200 ℃ at the speed of 5 ℃/min, and preserving the heat for 30 minutes in an oxygen atmosphere. And cooling to room temperature, heating to 800 ℃ at the speed of 10 ℃/min, preserving the heat for 15 minutes in the nitrogen atmosphere, and naturally cooling to room temperature to obtain the phosphorus-containing lithium battery cathode material.
The material described in example 7 and a metal lithium sheet were used as a positive electrode and a negative electrode, respectively, a 1mol/LLIPF6 solution was used as an electrolyte, a polypropylene microporous membrane was used as a separator, and the material was assembled into a CR2016 coin cell, which was used to characterize the electrical properties of the material described in example. The test results show that the material described in example 7 has a reversible charge capacity of 460mAh g -1 The initial coulombic efficiency is 83%, and the capacity retention rate of the material is more than 90% after 300 cycles under the constant current discharge rate of 0.5C.
Example 8
1) 0.45g of germanium powder was added to 8.65g of a N 'N-dimethylformamide/phytic acid mixed solution (8.425g of N' N-dimethylformamide and 0.225g of phytic acid), and stirred for 40 minutes.
2) 0.9g of homopolyacrylonitrile (Mw 150000) was weighed and added to the solution in step 1, and stirred at 50 ℃ until all the polymer was dissolved, to obtain a spinning solution.
3) And transferring the spinning solution into a 10ml needle cylinder, and collecting a precursor of the phosphorus-containing negative electrode material under the conditions that the positive voltage is 13.5KV, the negative voltage is-1.5 KV, the distance between a spinning port and a receiver is 15cm, and the injection speed of the spinning solution is 0.4 mm/min.
4) And (4) placing the precursor of the phosphorus-containing negative electrode material obtained in the step (3) in a tubular furnace, heating to 800 ℃ at the speed of 5 ℃/min, preserving the heat for 15 minutes in a nitrogen atmosphere, and naturally cooling to room temperature after the heat preservation, thus obtaining the phosphorus-containing lithium battery negative electrode material.
The material described in example 8 and a metal lithium sheet were used as a positive electrode and a negative electrode, respectively, a 1mol/LLIPF6 solution was used as an electrolyte, a polypropylene microporous membrane was used as a separator, and the material was assembled into a CR2016 coin cell, which was used to characterize the electrical properties of the material described in example. The test results show that the material described in example 8 has a reversible charge capacity of 780mAh g -1 The initial coulombic efficiency is 84%, and the capacity retention rate of the material is more than 90% after 200 cycles under the constant current discharge rate of 0.5C.
Example 9
1) 0.45g of germanium oxide was added to 8.65g of a N 'N-dimethylformamide/phosphoric acid mixed solution (8.425g of N' N-dimethylformamide and 0.225g of phosphoric acid), and stirred for 40 minutes.
2) 0.9g of homopolyacrylonitrile (Mw 150000) was weighed and added to the solution in step 1, and stirred at 50 ℃ until all the polymer was dissolved, to obtain a spinning solution.
3) And transferring the spinning solution into a 10ml needle cylinder, and collecting a precursor of the phosphorus-containing negative electrode material under the conditions that the positive voltage is 14KV, the negative voltage is-2.5 KV, the distance between a spinning opening and a receiver is 15cm, and the injection speed of the spinning solution is 0.4 mm/min.
4) Putting the precursor of the phosphorus-containing negative electrode material obtained in the step (3) into a tube furnace, heating to 1000 ℃ at the speed of 3 ℃/min, and reacting at H 2 And (3) preserving the heat for 30 minutes in the atmosphere of the/Ar mixed gas, and naturally cooling to room temperature after the heat preservation is finished to obtain the phosphorus-containing lithium battery cathode material.
The material described in example 9, a metal lithium sheet as a positive electrode and a negative electrode, a 1mol/LLIPF6 solution as an electrolyte, a polypropylene microporous membrane as a separator, and a CR2016 coin cell were assembled, respectively, to characterize the electrical properties of the material described in exampleCan be used. The test results show that the material described in example 9 has a reversible charge capacity of 810mAh g -1 The initial coulombic efficiency is 83%, and the capacity retention rate of the material is more than 92% after 200 cycles under the constant current discharge rate of 0.5C.
Example 10
1) Get D 50 0.45g of 120nm silica powder was added to 8.65g of an N 'N-dimethylformamide/polyphosphoric acid mixed solution (8.425g of N' N-dimethylformamide and 0.225g of polyphosphoric acid), and stirred for 90 minutes.
2) 0.9g of homopolyacrylonitrile (Mw 150000) was weighed and added to the solution in step 1, and stirred at 50 ℃ until all the polymer was dissolved, to obtain a spinning solution.
3) And transferring the spinning solution into a 10ml needle cylinder, and collecting a precursor of the phosphorus-containing negative electrode material under the conditions that the positive voltage is 13.5KV, the negative voltage is-1.5 KV, the distance between a spinning opening and a receiver is 13cm, and the injection speed of the spinning solution is 0.3 mm/min.
4) And (4) placing the precursor of the phosphorus-containing negative electrode material obtained in the step (3) in a tubular furnace, heating to 270 ℃ at the speed of 5 ℃/min, and preserving heat for 30 minutes in a nitrogen atmosphere. And then, heating to 800 ℃ at the speed of 10 ℃/min, preserving the heat for 15 minutes in the nitrogen atmosphere, and naturally cooling to room temperature after the heat preservation is finished to obtain the phosphorus-containing lithium battery cathode material.
The material described in example 10 and a metal lithium sheet were used as a positive electrode and a negative electrode, respectively, a 1mol/LLIPF6 solution was used as an electrolyte, a polypropylene microporous membrane was used as a separator, and the material was assembled into a CR2016 coin cell, which was used to characterize the electrical properties of the material described in example. The test results show that the material described in example 10 has a reversible charge capacity of 1080mAh g -1 The initial coulombic efficiency is 83%, and the capacity retention rate of the material is more than 90% after 120 cycles under the constant current discharge rate of 0.5C.
Comparative example 1
1) Get D 50 0.45g of 120nm silica powder was added to 8.65g of N' N-dimethylformamide and stirred for 90 minutes.
2) 0.9g of polyacrylonitrile copolymer (Mw 180000) was weighed and added to the solution in step 1, and stirred at 50 ℃ until all the polymer was dissolved, to obtain a spinning solution.
3) And transferring the spinning solution into a 10ml needle cylinder, and collecting a precursor of the phosphorus-containing negative electrode material under the conditions that the positive voltage is 11.5KV, the negative voltage is-2.5 KV, the distance between a spinning opening and a receiver is 15cm, and the injection speed of the spinning solution is 0.4 mm/min.
4) And (4) placing the precursor of the phosphorus-containing negative electrode material obtained in the step (3) in a tubular furnace, heating to 270 ℃ at the speed of 5 ℃/min, and preserving heat for 30 minutes in a nitrogen atmosphere. And then, heating to 800 ℃ at the speed of 10 ℃/min, preserving the heat for 15 minutes in the nitrogen atmosphere, and naturally cooling to room temperature after the heat preservation is finished to obtain the phosphorus-containing lithium battery cathode material. The negative electrode material is brittle and cannot be bent.
Fig. 10 and 11 are X-ray photoelectron spectra of C1s and Si2p of the negative electrode material for lithium battery in comparative example 1, respectively. The same C-O-P and Si-O-P functionality as in the sample described in example 1 is not present in comparative example 1 because no phosphorus-containing species is added.
The material described in comparative example 1, a metal lithium sheet as a positive electrode and a negative electrode, a 1mol/LLIPF6 solution as an electrolyte, and a polypropylene microporous membrane as a separator were assembled into a CR2016 coin cell, respectively, to characterize the electrical properties of the material described in the examples. The test results show that the material described in comparative example 1 has a reversible charge capacity of 1150mAh g -1 The initial coulombic efficiency is 69%, and after 30 cycles of the material under the constant current discharge rate of 0.5C, the capacity retention rate is 37% (as shown in figure 12), and the cycle stability performance is extremely poor. The comparison of the test results of the example 1 and the comparative example 1 proves that the phosphorus-containing buffer layer can effectively relieve the volume expansion of the electroactive substances in the material system and improve the cycling stability of the material.
The embodiments of the present invention are only used to illustrate the detailed process equipment and process flow of the present invention, but the present invention is not limited to the above detailed process equipment and process flow, i.e., the present invention can be implemented without depending on the steps of the embodiments. In conclusion, any modifications of the present invention, including the substitution of the raw materials and additives, the selection of the specific embodiments, etc., by those skilled in the art, are within the scope and disclosure of the present invention.

Claims (17)

1. The phosphorus-containing lithium ion battery cathode material is characterized by comprising a phosphorus element, an active component and carbon nanofibers;
the cathode material has a core-shell structure, the core comprises an active component, and the shell comprises a phosphorus element; the core-shell structure is loaded outside or/and inside the nano carbon fiber; the phosphorus element in the negative electrode material is connected with the active component through a chemical bond; and the phosphorus element in the negative electrode material is connected with the carbon nanofibers through chemical bonds.
2. The negative electrode material of claim 1, wherein the negative electrode material comprises a P (O) -O-R structural segment, and R comprises any one element of carbon, silicon, phosphorus, germanium, tin, vanadium and titanium.
3. The anode material of claim 1, wherein the active component of the anode material comprises any one or more of the elements silicon, germanium, tin, vanadium, and titanium.
4. The negative electrode material of claim 1, wherein the negative electrode material contains 0.1 to 12 parts by mass of phosphorus and 5 to 90 parts by mass of an active component, based on the parts by mass of the negative electrode material.
5. The negative electrode material according to claim 1, wherein the diameter of the carbon nanofibers in the negative electrode material is 50nm to 1 μm.
6. The negative electrode material according to claim 1, wherein the negative electrode material has a specific surface area of 1m 2 /g~1000m 2 /g。
7. The negative electrode material according to claim 6, wherein the specific surface area of the negative electrode material is 25m 2 /g~300m 2 /g。
8. The preparation process of the phosphorus-containing lithium ion battery negative electrode material as claimed in any one of claims 1 to 7, characterized by comprising the following steps:
1) contacting a phosphorus source with an active component for ultrasonic treatment to form a phosphorus-coated active component;
2) and (3) carrying out electrostatic spinning and heat treatment on the spinning solution containing the organic carbon source and the phosphorus-coated active component.
9. The preparation process of claim 8, wherein the organic carbon source in the preparation process comprises any one or more of cellulose acetate, chitosan, polyacrylic acid, polyvinylpyrrolidone, hydroxypropyl cellulose, polyester polyurethane, homopolyacrylonitrile, copoly-polyacrylonitrile, polyvinyl acetate, polyimide, polyamide, and modified asphalt.
10. The process according to claim 8, wherein the phosphorus source in the process comprises a compound containing a phosphoric acid group; the active component in the cathode material comprises one or more of silicon, germanium, tin, vanadium and titanium elements.
11. The process of claim 10, wherein the phosphorus source comprises any one or more of phytic acid, phosphoric acid, metaphosphoric acid, and polyphosphoric acid.
12. The preparation process according to claim 8, wherein the mass ratio of the phosphorus source to the active component in the preparation process is 1: 0.9-1: 36.
13. The preparation process according to claim 8, wherein the electrostatic spinning process parameters in the preparation process are positive voltage of 5 KV-30 KV and/or negative voltage of-0.2 KV-10 KV, and/or the distance between the spinning opening and the receiver is 5 cm-30 cm, and/or the injection speed of the spinning solution is 0.02mm/min-0.8 mm/min.
14. The preparation process according to claim 8, wherein the heat treatment in the preparation process comprises a step of roasting at 200-1200 ℃.
15. The process according to claim 14, wherein the heat treatment comprises a heat treatment step at 200 to 450 ℃ and a heat treatment step at 500 to 1200 ℃.
16. A lithium ion battery, comprising:
the phosphorus-containing lithium ion battery negative electrode material of claim 1 is used as a negative electrode;
a positive electrode material containing lithium element, a separator, and an electrolyte.
17. The battery of claim 16, wherein the lithium ion battery comprises any one of a liquid lithium ion battery, a semi-solid lithium ion battery, or an all-solid lithium ion battery.
CN201910378696.4A 2019-05-08 2019-05-08 Phosphorus-containing lithium ion battery cathode material and preparation process thereof Active CN111916686B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201910378696.4A CN111916686B (en) 2019-05-08 2019-05-08 Phosphorus-containing lithium ion battery cathode material and preparation process thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201910378696.4A CN111916686B (en) 2019-05-08 2019-05-08 Phosphorus-containing lithium ion battery cathode material and preparation process thereof

Publications (2)

Publication Number Publication Date
CN111916686A CN111916686A (en) 2020-11-10
CN111916686B true CN111916686B (en) 2022-08-12

Family

ID=73242978

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201910378696.4A Active CN111916686B (en) 2019-05-08 2019-05-08 Phosphorus-containing lithium ion battery cathode material and preparation process thereof

Country Status (1)

Country Link
CN (1) CN111916686B (en)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112635745B (en) * 2019-10-09 2022-10-11 中国石油化工股份有限公司 Composite material, preparation method thereof, lithium battery cathode and lithium battery
EP4044278A4 (en) * 2019-10-09 2024-01-03 China Petroleum & Chem Corp Negative electrode material, preparation method therefor, and application thereof, and lithium ion battery comprising same
CN114075717B (en) * 2021-11-11 2023-03-21 大连理工大学 Method for preparing tin phosphide/carbon black nanofiber self-supporting negative electrode material through electrostatic spinning and application of tin phosphide/carbon black nanofiber self-supporting negative electrode material

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101740752A (en) * 2009-12-16 2010-06-16 深圳市德方纳米科技有限公司 Core-shell composite anode material for lithium ion battery and preparation method thereof
CN105006547A (en) * 2014-07-30 2015-10-28 香港应用科技研究院有限公司 Lithium-ion battery and coating method of electrode active material of lithium-ion battery
KR20160122009A (en) * 2015-04-13 2016-10-21 한국과학기술연구원 Catalyst comprising Co-P core and carbon shell for alkaline oxygen reduction reaction and its preparation method

Family Cites Families (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030152835A1 (en) * 2002-02-08 2003-08-14 Sankar Dasgupta Carbon fibre containing negative electrode for lithium battery
US7879442B2 (en) * 2003-09-16 2011-02-01 Showa Denko K.K. Composite of vapor grown carbon fiber and inorganic fine particle and use thereof
US20140370380A9 (en) * 2009-05-07 2014-12-18 Yi Cui Core-shell high capacity nanowires for battery electrodes
CN103229334A (en) * 2010-11-29 2013-07-31 株式会社新王材料 Secondary battery negative electrode material, secondary battery negative electrode, process for production of secondary battery negative electrode material, and process for production of secondary battery negative electrode
JP6186568B2 (en) * 2013-08-26 2017-08-30 国立研究開発法人産業技術総合研究所 One-dimensional nanostructure for electrochemical device electrode material, manufacturing method by electrospinning method
CN103977825B (en) * 2014-05-14 2015-11-18 西北工业大学 A kind of phosphorus doping porous carbon catalyst and preparation method
CN105789640A (en) * 2014-12-16 2016-07-20 中国科学院大连化学物理研究所 Application of carbon nanofiber and metal composite electrode in flow battery
CN105226296B (en) * 2015-09-18 2017-05-03 哈尔滨工业大学 Nitrogen and phosphorus co-doped cobalt-based carbon fiber multifunctional electrochemical catalyst and preparation method thereof
CN105552313A (en) * 2015-12-17 2016-05-04 天津大学 Preparation method of biochemical humic acid-based carbon nanofiber electrode
CN106099055B (en) * 2016-06-20 2017-10-20 三峡大学 A kind of preparation method of the flexible carbon-fiber film negative material of nitrogen-phosphor codoping
CN106129367A (en) * 2016-08-22 2016-11-16 浙江理工大学 A kind of silicon/carbon nano-composite fiber and application thereof
CN106784615B (en) * 2016-11-18 2020-08-04 深圳大学 Flexible lithium ion battery cathode, preparation method thereof and flexible lithium ion battery
CN107159282A (en) * 2017-03-28 2017-09-15 江苏师范大学 A kind of carbon fiber loaded CoWP catalyst and preparation method
CN109473633B (en) * 2017-09-07 2021-06-11 上海杉杉科技有限公司 Nano silicon-based composite fiber negative electrode material of lithium ion battery and preparation method of nano silicon-based composite fiber negative electrode material
CN108682816A (en) * 2018-05-18 2018-10-19 华中科技大学 A kind of high face carrying capacity lithium sulphur composite positive pole and preparation method thereof
CN108760847B (en) * 2018-06-07 2020-04-17 海南师范大学 Method for preparing zinc oxide-carbon nanofiber composite material and modified electrode thereof by electrostatic spinning and high-temperature carbonization method

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101740752A (en) * 2009-12-16 2010-06-16 深圳市德方纳米科技有限公司 Core-shell composite anode material for lithium ion battery and preparation method thereof
CN105006547A (en) * 2014-07-30 2015-10-28 香港应用科技研究院有限公司 Lithium-ion battery and coating method of electrode active material of lithium-ion battery
KR20160122009A (en) * 2015-04-13 2016-10-21 한국과학기술연구원 Catalyst comprising Co-P core and carbon shell for alkaline oxygen reduction reaction and its preparation method

Also Published As

Publication number Publication date
CN111916686A (en) 2020-11-10

Similar Documents

Publication Publication Date Title
US10450674B2 (en) Process for preparing a silicon-carbon nanocomposite nanofiber
CN107681142B (en) Molybdenum disulfide coated carbon nanofiber used as lithium ion battery negative electrode material and preparation method thereof
CN111916686B (en) Phosphorus-containing lithium ion battery cathode material and preparation process thereof
Wu et al. PVDF-HFP/PET/PVDF-HFP composite membrane for lithium-ion power batteries
CN110616561B (en) Novel method for preparing carbon nano tube/carbon nano fiber composite material film
KR101341951B1 (en) Silicon-carbon composite for negative electrode of lithium secondary battery
Weng et al. Electrospun carbon nanofiber-based composites for lithium-ion batteries: structure optimization towards high performance
CN102074683A (en) Porous carbon nanofiber anode material for lithium ion battery and preparation method thereof
CN111900411B (en) Self-supporting silicon-carbon negative electrode material and preparation method thereof
CN105226253A (en) A kind of silicon nanoparticle-graphite flake-carbon nano tube compound material and preparation method thereof and application
CN110071261A (en) The preparation method of battery electrode
CN112635762B (en) Lithium ion battery negative electrode material, preparation method and application thereof, and lithium ion battery
CN114447291B (en) Self-supporting ferric trifluoride-carbon nanofiber anode material and preparation method thereof
CN108807903B (en) Preparation method of composite modified lithium battery negative electrode material for lithium battery
CN114242987A (en) Preparation method of three-dimensional porous silicon-carbon composite material
CN114171736A (en) Water-based lithium manganate positive electrode slurry and preparation method thereof
CN113422009A (en) Lithium ion battery cathode material and preparation method and application thereof
CN111129394B (en) Functional composite type carbon nanofiber/graphene membrane as well as preparation method and application thereof
CN111916750B (en) Enhanced self-supporting lithium ion battery cathode material and preparation process thereof
CN107994232B (en) Carrier material for lithium-sulfur battery
CN114023924B (en) Preparation method of silicon-based negative electrode without current collector and fiber lithium ion battery
CN114824239A (en) Tin-antimony oxide composite material, preparation method thereof and application thereof in preparation of battery cathode
CN111916725B (en) Phosphorus-doped high-nickel cathode material for lithium battery and preparation process thereof
Zhao et al. Application Progress and Practical Evaluations of Nanofiber Nonwoven Fabrics for Flexible/wearable Batteries
CN111041709A (en) PVDF nanofiber membrane with through hole structure and preparation method 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