CN116960329A - Negative electrode material and preparation method and application thereof - Google Patents
Negative electrode material and preparation method and application thereof Download PDFInfo
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- CN116960329A CN116960329A CN202310658595.9A CN202310658595A CN116960329A CN 116960329 A CN116960329 A CN 116960329A CN 202310658595 A CN202310658595 A CN 202310658595A CN 116960329 A CN116960329 A CN 116960329A
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- negative electrode
- anode material
- electrode material
- hard carbon
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- 239000007773 negative electrode material Substances 0.000 title claims abstract description 88
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 229910021385 hard carbon Inorganic materials 0.000 claims abstract description 60
- 125000005842 heteroatom Chemical group 0.000 claims abstract description 59
- 239000010405 anode material Substances 0.000 claims description 91
- 239000011148 porous material Substances 0.000 claims description 49
- 239000003431 cross linking reagent Substances 0.000 claims description 32
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 31
- 229910052799 carbon Inorganic materials 0.000 claims description 27
- 238000004132 cross linking Methods 0.000 claims description 21
- 239000010410 layer Substances 0.000 claims description 16
- 239000003792 electrolyte Substances 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 239000011229 interlayer Substances 0.000 claims description 14
- 239000011164 primary particle Substances 0.000 claims description 12
- 239000007833 carbon precursor Substances 0.000 claims description 10
- 239000011163 secondary particle Substances 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
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- 229910001415 sodium ion Inorganic materials 0.000 abstract description 30
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 abstract description 15
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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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
-
- 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
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The application relates to the technical field of negative electrode materials of sodium ion batteries, and provides a negative electrode material, a preparation method and application thereof. The negative electrode material provided by the application comprises a hard carbon three-dimensional porous structure, wherein at least part of the skeleton of the hard carbon three-dimensional porous structure is a block skeleton containing hetero atoms. The three-dimensional framework structure of the negative electrode material provided by the application endows the negative electrode material with abundant defects and active centers, so that a sodium ion transmission path and an electron conduction diffusion path can be effectively shortened, and the negative electrode material shows excellent sodium storage performance and conductivity.
Description
Technical Field
The application belongs to the technical field of negative electrode materials of sodium ion batteries, and particularly relates to a negative electrode material, a preparation method and application thereof.
Background
The sodium ion battery and the lithium ion battery have the same working principle and belong to secondary batteries. The sodium ion battery has higher stability, is less prone to thermal runaway and other conditions, and is rich in sodium resources, so that the sodium ion battery is widely focused.
However, because of the limitation of the radius of sodium ions, the interlayer spacing of the conventional graphite negative electrode is insufficient to allow free intercalation of sodium ions having a larger radius between the layers, and therefore, development of a negative electrode material suitable for sodium ion batteries is desired.
Hard carbon refers to carbon which is difficult to graphitize, and compared with conventional graphite, the hard carbon has a highly disordered structure and large interlayer spacing, and can meet the requirement of free intercalation and deintercalation of sodium ions between layers, so that the hard carbon has excellent sodium storage capacity. However, the sodium ion battery made of hard carbon is poor in rate performance and cycle stability, and it is difficult to meet the increasing high capacity demand of people for secondary batteries.
Disclosure of Invention
The application aims to provide a negative electrode material and a preparation method thereof, and aims to solve the problem that the existing negative electrode material is poor in rate capability and cycle stability.
Another object of the present application is to provide a negative electrode and a secondary battery including the same, which aims to solve the problems of non-ideal capacity, rate performance and cycle stability of the secondary battery.
In order to achieve the purposes of the application, the technical scheme adopted by the application is as follows:
in a first aspect, the present application provides a negative electrode material comprising a hard carbon three-dimensional porous structure, wherein at least part of the skeleton of the hard carbon three-dimensional porous structure is a block skeleton comprising heteroatoms.
In a second aspect, the present application provides a method for preparing a negative electrode material, comprising the steps of:
step S10, providing a carbon source and a cross-linking agent containing hetero atoms;
step S20, dispersing a carbon source and a crosslinking agent into a solvent, and performing a crosslinking reaction after desolvation treatment to obtain a hard carbon precursor with a three-dimensional structure;
and step S30, carbonizing the hard carbon precursor to obtain the anode material.
In a third aspect, the present application provides a negative electrode comprising a current collector and a negative electrode active material layer bonded to the surface of the current collector, the negative electrode active material layer comprising the negative electrode material of the present application or a negative electrode material produced by the method for producing a negative electrode material of the present application.
In a fourth aspect, the application provides a secondary battery comprising a positive plate, a negative plate, a diaphragm and electrolyte, wherein the negative plate is the negative electrode of the application.
The anode material provided by the first aspect of the application has a hard carbon three-dimensional porous structure formed by interconnecting carbon atoms and heteroatoms and interconnecting carbon atoms, and the skeleton of the hard carbon three-dimensional porous structure also comprises a block skeleton of the heteroatoms, so that the anode material is endowed with abundant defects and active centers, and the sodium ion transmission path and the electron conduction diffusion path can be effectively shortened, so that the anode material shows excellent sodium storage performance and conductivity, and therefore, the anode material has higher electrochemical performances such as specific capacity, rate performance, cycling stability and the like.
According to the preparation method of the anode material, provided by the second aspect of the application, the cross-linking agent containing hetero atoms is used as a block framework to perform condensation cross-linking reaction with the carbon source, so that the carbon source is expanded to a three-dimensional space through cross-linking modification, the cross-linking agent induces the carbon source to form a hard carbon precursor with a three-dimensional structure, the three-dimensional structure contains the hetero atom block framework, and then hetero atoms contained in the cross-linking agent enter the three-dimensional structure in the carbonization process, so that a multi-stage porous structure is formed, and the anode material is endowed with higher specific capacity, rate capability and cycle stability. In addition, the preparation method of the anode material can effectively prepare the anode material with stable structure and electrochemical performance, and the preparation process is simple, low in cost and suitable for mass industrialized production and application.
The negative electrode provided by the third aspect of the application has the advantages that the negative electrode material is provided with the three-dimensional framework structure formed by interconnecting carbon atoms and heteroatoms, so that the sodium storage performance, the multiplying power performance and the cycle stability of the negative electrode can be effectively improved, and the negative electrode material is safe to use and long in service life.
The secondary battery provided by the fourth aspect of the application has higher capacity, rate capability and cycle stability because of the inclusion of the negative electrode provided by the application.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are needed in the embodiments or the description of the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present application, and that other drawings can be obtained according to these drawings without inventive effort for a person skilled in the art.
Fig. 1 is a schematic flow chart of a preparation method of a negative electrode material according to an embodiment of the present application;
FIG. 2 is a scanning electron micrograph of the negative electrode material provided in example 1 of the present application;
FIG. 3 is an X-ray energy spectrum electron photograph of the anode material provided in example 1 of the present application;
fig. 4 is an X-ray diffraction pattern of the negative electrode material provided in example 1 of the present application.
Detailed Description
In order to make the technical problems, technical schemes and beneficial effects to be solved more clear, the application is further described in detail below with reference to the embodiments. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the application.
In the present application, the term "and/or" describes an association relationship of an association object, which means that three relationships may exist, for example, a and/or B may mean: a alone, a and B together, and B alone. Wherein A, B may be singular or plural. The character "/" generally indicates that the context-dependent object is an "or" relationship.
In the present application, "at least one" means one or more, and "a plurality" means two or more. "at least one of" or the like means any combination of these items, including any combination of single item(s) or plural items(s). For example, "at least one (individual) of a, b, or c," or "at least one (individual) of a, b, and c," may each represent: a, b, c, a-b (i.e., a and b), a-c, b-c, or a-b-c, wherein a, b, c may be single or multiple, respectively.
It should be understood that, in various embodiments of the present application, the sequence number of each process described above does not mean that the execution sequence of some or all of the steps may be executed in parallel or executed sequentially, and the execution sequence of each process should be determined by its functions and internal logic, and should not constitute any limitation on the implementation process of the embodiments of the present application.
The terminology used in the embodiments of the application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. As used in this application and the appended claims, the singular forms "a," "an," and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise.
The weights of the relevant components mentioned in the description of the embodiments of the present application may refer not only to the specific contents of the components, but also to the proportional relationship between the weights of the components, so long as the contents of the relevant components in the description of the embodiments of the present application are scaled up or down within the scope of the disclosure of the embodiments of the present application. Specifically, the mass described in the specification of the embodiment of the application can be mass units known in the chemical industry field such as mu g, mg, g, kg.
The terms "first" and "second" are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or implicitly indicating the number of technical features indicated for distinguishing between objects such as substances from each other. For example, a first XX may also be referred to as a second XX, and similarly, a second XX may also be referred to as a first XX, without departing from the scope of embodiments of the application. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include one or more such feature.
According to a first aspect of the embodiment of the application, a negative electrode material is provided, which comprises a hard carbon three-dimensional porous structure, wherein at least part of the framework of the hard carbon three-dimensional porous structure is a block framework containing hetero atoms. It is understood that the block backbone is a heteroatom-forming linked backbone formed in a three-dimensional porous structure.
The anode material provided by the first aspect of the embodiment of the application has a hard carbon three-dimensional porous structure formed by interconnecting carbon atoms and heteroatoms and interconnecting carbon atoms, and the skeleton of the three-dimensional porous structure also comprises a block skeleton of the heteroatoms, so that the anode material is endowed with abundant defects and active centers, and the sodium ion transmission path and the electron conduction diffusion path can be effectively shortened, so that the anode material shows excellent sodium storage performance and conductivity, and therefore, the anode material has higher electrochemical performances such as specific capacity, rate performance, cycling stability and the like.
It is understood that heteroatom, strictly speaking, refers to any atom that is not carbon or hydrogen. Heteroatoms in embodiments of the present application refer to non-carbon atoms substituted for carbon atoms at certain lattice sites in the backbone of the molecular structure.
In some embodiments, the skeleton of the hard carbon three-dimensional porous structure is uniformly doped with heteroatoms. Specifically, carbon atoms and hetero atoms are connected through chemical bonds to form a three-dimensional porous skeleton, wherein the carbon atoms are nodes, the hetero atoms are connected with the carbon atoms through M-C bonds or M-O-C bonds, M refers to the hetero atoms, that is, the hetero atoms are uniformly doped in the carbon chain skeleton of the three-dimensional structure after cross-linking, and the skeleton structure is distinguished from a block skeleton directly formed by the hetero atoms. The hetero atoms distributed in the three-dimensional porous structure of the hard carbon can further increase defect sites and interlayer spacing of the hard carbon, effectively enhance the adsorption performance of active ions, promote intercalation and diffusion of the active ions, and further improve the sodium storage capacity of the anode material.
In some embodiments, the skeleton of the hard carbon three-dimensional porous structure is bounded by carbon atoms. It should be understood that nodes, in general, refer to localized expansions (like individual knots), or a junction. In the embodiment of the application, a node refers to an interconnection common point of two or more branches in a three-dimensional framework structure, wherein the branches refer to chemical bonds formed by connection of heteroatoms and carbon atoms. The three-dimensional framework structure takes carbon atoms as nodes, so that the stability of the framework structure is fully ensured, collapse of the framework structure is avoided, and higher cycle stability of the anode material is endowed.
In some embodiments, the heteroatom includes at least one of N, O, S, P, B, F. The heteroatom provided by the embodiment of the application can increase the interlayer spacing of the hard carbon, so that the anode material not only has sufficient interlayer spacing to meet the intercalation and deintercalation of active ions, but also can further increase defect sites of the hard carbon, thereby enhancing the adsorption of the active ions and promoting the intercalation and diffusion of the active ions. The radius of N, O, S, P, F is higher than that of C, so that the expansion of the spacing between hard carbon layers can be effectively realized, and meanwhile, the negative electrode material with the three-dimensional porous skeleton structure has a stable structure in the charge and discharge process; the radius of the B element is close to that of the C element, and the doping of the B element reduces the lattice deformation of the anode material in the charge and discharge process, so that the structural stability of the anode material is improved.
In some embodiments, the heteroatoms comprise 0.01 to 15wt% of the total mass of the anode material. If the content of the hetero atoms is too large, the more defects are formed in the hard carbon, the higher the consumption of active ions is when an SEI film (Solid Electrolyte Interface, solid electrolyte interface film) is formed, and the lower the first coulombic efficiency of the anode material is easily caused; if the content of the hetero atoms is too small, a three-dimensional framework structure is difficult to form, the pore structure formed in the anode material is small, the conductivity and the specific capacity of the anode material are not improved, the interlayer spacing of the hard carbon is not increased obviously, and the quick charge performance of the anode material is affected. In addition, the mass ratio of the hetero atoms can also realize the adjustment of the pore structure contained in the three-dimensional framework structure, thereby realizing the effective improvement of the capacity and the multiplying power performance of the anode material.
Specifically, the heteroatom may account for 0.01wt%, 0.05wt%, 0.1wt%, 0.5wt%, 1wt%, 3wt%, 5wt%, 8wt%, 10wt%, 12wt%, 13wt%, 15wt% or be in a range composed of any of the above values, based on the total mass of the anode material. The proportion of the hetero atoms has an adjusting effect on the three-dimensional porous structure formed by the whole, particularly the specific surface area and the pore volume of the hetero atoms are adjusted on the whole material, if the hetero atoms are lower than the lower limit of the range, the cross-linking agent is possibly insufficient, on one hand, the cross-linking effect cannot reach the preset effect, and on the other hand, the specific surface area and the pore volume of the whole material cannot be expanded to the effective range; if the heteroatom exceeds the above range, the defects of the whole structure are excessive, and the SEI film effect is excessive under the condition of the excessive specific surface area, so that the first coulomb effect is influenced; thus, a choice within the range is the most balanced preferred ratio.
In some embodiments, the hard carbon three-dimensional porous structure comprises interconnected multi-stage mesh. In the porous structure, the formed pore structures are mutually communicated, so that the anode material has rich pore structures, higher active ion adsorption capacity is given to the anode material, and the infiltration of electrolyte is facilitated, so that the conductivity and specific capacity of the anode material are improved.
In some embodiments, the multi-stage mesh comprises micropores, mesopores, and macropores. The carbon atoms and the hetero atoms in the anode material are connected with each other to form a three-dimensional framework structure, and the structure has more pores with inconsistent pore diameters and can be divided into micropores, mesopores and macropores according to the pore diameters. The micropores, the mesopores and the macropores are mutually communicated. At least a plurality of mesopores are communicated between adjacent macropores, and the structure of the macropores connected with the mesopores can be used as a buffer of electrolyte so as to promote active ions to smoothly enter pore channels; at least a plurality of micropores are communicated between the adjacent macropores, and the abundant micropores can provide abundant active sites for adsorption and filling of active ions in the macropore pore canal.
It should be understood that the pore sizes of the micropores, mesopores and macropores in the examples of the present application conform to the international association of pure and applied chemistry (IUPAC). According to the definition of the international association of pure and applied chemistry (IUPAC), pore width, i.e. the pore diameter (for cylindrical pores) or the distance between two opposite pore walls (for slit pores), micropore refers to pores with an internal pore width of less than 2 nm; mesoporous means pores with a pore width of between 2nm and 50nm, macroporous means pores with a pore width of more than 50nm and an upper limit of 100 nm.
In some embodiments, the micropores have a pore size of < 2nm, and the micropores comprise 10-40% of the number of pores contained in the negative electrode material. The adsorption capacity of the micropores is high, and the contact area between the electrolyte and the active material can be ensured to be larger, so that the infiltration of the electrolyte is facilitated. The cathode material has proper specific surface area within the range of the micropore quantity ratio provided by the embodiment of the application, so that the consumption of active ions in the SEI film formation process is reduced. Specifically, the proportion of micropores to the number of micropores contained in the anode material may be 10%, 15%, 16%, 17%, 18%, 19%, 20%, 22%, 25%, 27%, 29%, 30%, 35%, 40% or within a range composed of any of the above values. Micropores are structural compositions which mainly provide a high specific surface area, and if the overall proportion of the micropores is smaller than the value of the defined range, the specific surface area provided is limited, and good contact effect with the electrolyte and the active substance cannot be achieved; and when the ratio exceeds the range, an excessively large specific surface area is easily obtained, and active ions consumed by the SEI film are excessively large.
In some embodiments, the mesopores have a pore size of 2-50 nm and represent 40-80% of the number of pores contained in the anode material. The mesoporous can effectively promote the rapid diffusion of electrons and sodium ions, thereby improving the conductivity and the rapid charging performance of the anode material. Specifically, the proportion of the mesopores to the number of the pores contained in the anode material may be 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80% or within a range composed of any of the above values. The mesopores are used as main diffusion structure channels of sodium ions, if the mesopores are too little in distribution, the quantity of sodium ions stored in macropores cannot be received, and the micropore structure cannot be fully utilized so that the electrolyte is fully contacted with the active material; in the range, the mesoporous distribution ratio can be more proper, so that the structural distribution of the multistage holes can be fully and cooperatively utilized.
In some embodiments, the macropores have a pore diameter of 50-100 nm, and the macropores account for 1-15% of the number of pores contained in the negative electrode material. The macropores can act as a reservoir to facilitate high rate storage of more sodium ions, thereby imparting higher conductivity and specific capacity to the anode material. Specifically, the proportion of macropores to the number of pores contained in the anode material may be 1%, 3%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15% or be within a range composed of any of the above values. Specifically, the macropores are mainly used as a reservoir layer, and the structural form of the macropores exists on the surface of the outer layer of the primary particles, so that high-speed storage of sodium ions can be promoted, namely, the macropores are positioned on the surface, the mesopores and the micropores are positioned in the multi-stage mesh structure, if the ratio of the macropores is too small, the effects of storage and high-speed migration of sodium ions cannot be achieved, and if the ratio of the macropores is too large, the distribution positions of the micropores and the mesopores are extruded, so that the specific capacity is reduced.
In some embodiments, the primary particle size of the negative electrode material is 50 to 700nm. The primary particle size refers to the particle size of individual particles of the anode material under microscopic test conditions, i.e., the individual microscopic particle size. The primary particle size of the anode material is nano-scale, the particle size is small, the infiltration of electrolyte is facilitated, and the transmission speed of active ions is improved, so that the anode material is endowed with higher conductivity and gram capacity. Specifically, the primary particle diameter of the anode material may be 50 to 100nm, or 100 to 150nm, or 150 to 200nm, or 200 to 250nm, or 250 to 300nm, or 300 to 350nm, or 350 to 400nm, or 400 to 450nm, or 450 to 500nm, or 500 to 600nm, or 600 to 700nm.
In some embodiments, the secondary particle size of the anode material is 0.5 to 100 μm. The secondary particle size refers to the size of bulk particles formed after crosslinking and stacking of single particles of the anode material, namely the particle size of macroparticles formed after crosslinking of a plurality of primary particles. The macro particles of the anode material are of a micron level, so that the diffusion distance of active ions in the hard carbon material is shortened, and the energy density is improved when the active ions are applied to the anode of the secondary battery. In some embodiments, the secondary particle size of the anode material may be 0.5 to 1 μm, or 1 to 10 μm, or 10 to 20 μm, or 20 to 30 μm, or 30 to 40 μm, or 40 to 50 μm, or 50 to 60 μm, or 60 to 70 μm, or 70 to 80 μm, or 80 to 90 μm, or 90 to 100 μm. Under the same particle size design of the secondary particles, if the median particle size of the primary particles is too small, the number of the primary particles forming the secondary particles of the material is increased, so that the specific surface area of the secondary particles is increased, and particularly for the multi-stage porous three-dimensional structure of the material, the area where side reaction occurs is increased; meanwhile, in the tabletting process of the pole piece, secondary particles containing excessive primary particles are easy to break, so that new interfaces appear in a further step, and the battery performance is deteriorated. In addition, the excessively large median particle diameter of the primary particles can directly increase the diffusion path of sodium ions in the secondary particle material, so that the capacity of the material is exerted to be low, the battery impedance is increased, and the power performance is reduced. The aggregate has a median particle diameter within the above range, and thus, the secondary reaction with the electrolyte is prevented from increasing due to too small primary particles of the aggregate, and further, the structural stability of the aggregate is prevented from deteriorating. In addition, the diffusion path of sodium ions in the agglomerates can be more suitable, so that the rate performance of the battery is better.
In some embodiments, the pore volume of the anode material is 0.01-0.8 cm 3 And/g. Pore volume refers to the total volume of pores per unit mass of porous solid that can be tested using methods known in the art. In the hole Rong Fanwei provided by the embodiment of the application, the anode material has a proper specific surface area, which is more beneficial to improving the efficiency of the intercalation and deintercalation of active ions, thereby having higher conductivity and capacity. In some embodiments, the pore volume of the anode material may be 0.01cm 3 /g、0.05cm 3 /g、0.1cm 3 /g、0.2cm 3 /g、0.3cm 3 /g、0.4cm 3 /g、0.5cm 3 /g、0.6cm 3 /g、0.7cm 3 /g、0.8cm 3 /g orWithin the range of any of the values above. Since the structure of the present application has a large number of micropores, and when the cumulative pore volume of the micropores is too small in the size range of 0.01 μm or more and 1 μm or less, the electrolyte cannot penetrate into the particles, and the insertion and detachment sites of sodium ions in the particles cannot be effectively utilized, so that it is difficult to smoothly perform insertion and detachment of sodium ions at the time of rapid charge and discharge. On the other hand, when the content is within the above range, the electrolyte can smoothly and effectively spread inside the particles, and therefore, at the time of charge and discharge, not only sodium ions in the outer peripheral portion of the particles can be effectively and efficiently utilized to insert and release sites through mesopores, but also sodium ions existing inside the particles can be effectively and efficiently utilized to insert and release sites, thereby improving electrochemical performance.
In some embodiments, the specific surface area of the anode material is 0.5-1000 m 2 And/g. It is understood that the specific surface area refers to the total area that a mass of material has. The larger the specific surface area of the negative electrode material, the more the polarization reaction is, so that the more active ions are needed for forming the first SEI film, the more active ions are lost, and the lower the first coulombic efficiency of the negative electrode material is. In addition, the larger the specific surface area of the anode material, the more binder is required to form the anode active material layer, resulting in the anode active material layer having higher internal resistance. In the specific surface area range of the anode material provided by the embodiment of the application, the irreversible sodium ion amount consumed by generating the SEI film in the initial sodium deintercalation process is reduced when the anode material is applied to the anode material of a sodium ion battery, the consumption of a binder in an anode active material layer can be reduced, and the anode material is endowed with higher first coulombic efficiency, first charge-discharge capacity and safety. Specifically, the specific surface area of the anode material may be 0.5 to 5m 2 Per gram, or 5-10 m 2 Per gram, or 10-50 m 2 Per gram, or 50-100 m 2 Per gram, or 100-200 m 2 Per gram, or 200-500 m 2 Per gram, or 500-700 m 2 Per gram, or 700-1000 m 2 /g。
In some embodiments, d of the anode material 002 The interlayer spacing of the crystal face is 0.370-0.410 nm. d, d 002 The crystal plane refers to the hard carbon (002) The interplanar spacing is measured by X-ray diffraction method and used for representing the size of the spacing between the hard carbon layers. Hard carbon d provided in the embodiment of the application 002 The interlayer spacing of the crystal face is in a range, so that free intercalation and deintercalation of active ions between hard carbon layers are facilitated, the transmission speed of the active ions is effectively improved, and the anode material is endowed with higher capacity and rate capability. Specifically, d of the negative electrode material 002 The interlayer spacing of the crystal planes is 0.37nm,0.38nm,0.39nm,0.40nm,0.41nm or within a range consisting of any of the above values.
In some embodiments, the peak intensity I of the D-band of the negative electrode material D Peak intensity I with G band G The ratio of the two is 0.8-1.9. It should be understood that I D Means that the D peak (1350 cm) of the hard carbon anode material is tested by Raman spectrum -1 Left and right), peak intensity, I G Refers to the G peak (1580 cm) -1 Left and right), peak intensity, I D /I G Values are used to characterize the order of the hard carbon anode material. Wherein the D peak reflects the degree of lattice defect and structural irregularity of hard carbon, and the G peak represents SP 2 The in-plane stretching vibration quantity of the hybridized carbon atoms reflects the order degree of the anode material. I provided in embodiments of the present application D /I G In the value range, it is considered that the negative electrode material has an appropriate defect degree, which is more advantageous for improving the capacity exertion of the hard carbon material and giving a higher specific capacity to the negative electrode material.
A second aspect of the embodiment of the present application provides a method for preparing a negative electrode material, as shown in fig. 1, including the following steps:
step S10, providing a carbon source and a cross-linking agent containing hetero atoms;
step S20, dispersing a carbon source and a crosslinking agent into a solvent, and performing a crosslinking reaction after desolvation treatment to obtain a hard carbon precursor with a three-dimensional structure;
and step S30, carbonizing the hard carbon precursor to obtain the anode material.
According to the preparation method of the anode material provided by the embodiment of the application, the cross-linking agent containing hetero atoms is used as a block framework to perform condensation cross-linking reaction with the carbon source, so that the carbon source is expanded to a three-dimensional space through cross-linking modification, the cross-linking agent induces the carbon source to form a hard carbon precursor with a three-dimensional structure, the three-dimensional structure contains the hetero atom block framework, and then hetero atoms contained in the cross-linking agent enter the three-dimensional structure in the carbonization process to form a multi-stage porous structure, so that the anode material is endowed with higher specific capacity, rate capability and cycle stability. In addition, the preparation method of the anode material can effectively prepare the anode material with stable structure and electrochemical performance, and the preparation process is simple, low in cost and suitable for mass industrialized production and application.
It is understood that in step S10, the heteroatom refers strictly to any atom which is not carbon or hydrogen. Heteroatoms in embodiments of the present application refer to non-carbon atoms substituted for carbon atoms at certain lattice sites in the backbone of the molecular structure.
In some embodiments, in step S10, the heteroatoms in the crosslinker include at least one of nitrogen, oxygen, sulfur, phosphorus, boron, fluorine. In the embodiment of the application, the hetero atoms come from the cross-linking agent, a hetero atom block skeleton is formed in the three-dimensional structure in the cross-linking process, and hetero atom doping is formed in the three-dimensional structure in the carbonization process.
In some specific embodiments, in step S10, the cross-linking agent comprises at least one of citric acid, oxalic acid, melamine, phosphoric acid, phytic acid, p-toluenesulfonic acid, p-phenylenediamine, ningkan anhydride, isophorone diisocyanate, hexamethylene diisocyanate, 2, 3-dimethylmaleic anhydride, sulfuric acid, diammonium phosphate, benzidine disulfonate, metaphenylene disulfonic acid, 3, 4-thiophenedicarboxylic acid, succinic acid, 1,3, 5-triaminobenzene, 2, 4-diaminobenzenesulfonic acid, 5-sulfoisophthalic acid, (4-aminophenyl) phosphonic acid, 4-carboxyphenylboronic acid, 1, 3-aminophenylboronic acid, 4-boranesulfuric acid, phenyldiboronic acid, dibenzothiophene-2, 8-diboronic acid.
In some embodiments, in step S10, the carbon source comprises at least one of lignin, cellulose, sugar, resin, starch, pitch.
Specifically, the saccharide includes at least one of fructose and glucose.
Specifically, the resin comprises at least one of epoxy resin, phenolic resin, furfural resin and urea-formaldehyde resin.
Specifically, the starch comprises at least one of corn starch, sweet potato starch and potato starch.
Specifically, the asphalt comprises at least one of petroleum asphalt, coal tar asphalt and natural asphalt.
In some embodiments, in step S20, the mass ratio of the carbon source, the cross-linking agent, and the solvent is 100:0.01-20:50-200. The addition amount of the solvent should be sufficient, so that the uniform mixing of the carbon source and the cross-linking agent can be ensured, and the subsequent removal of the solvent is facilitated. If the addition amount of the cross-linking agent is too low, the cross-linking coupling between the carbon source and the cross-linking agent is insufficient, so that hetero atoms contained in the hard carbon are too low, the hetero atoms and the carbon atoms are difficult to form a three-dimensional framework structure, defects and active sites in the negative electrode material are too few, the interlayer spacing of the hard carbon is too low, the storage and the intercalation and deintercalation of active ions are not facilitated, the conductivity of the negative electrode material is insufficient, and the impedance is large. If the addition amount of the cross-linking agent is too high, the more defects are formed in the hard carbon, the larger the area of the SEI film formed on the surface of the anode material particles is in the first charging process, the more active ions are lost, and therefore the first coulombic efficiency is low.
In some embodiments, the mass ratio of carbon source to crosslinker may be 100:0.01, or 100:0.05, or 100:0.1, or 100:1, or 100:5, or 100:10, or 100:15, or 100:20.
In some embodiments, in step S20, the desolvation treatment includes a heat treatment at 80-100 ℃. The solvent removal treatment aims at enabling the carbon source and the cross-linking agent to be uniformly mixed and providing a basis for the subsequent cross-linking reaction. In some embodiments, the desolvation treatment temperature may be 80 ℃, 85 ℃, 90 ℃, 95 ℃, 100 ℃, or within a range consisting of any of the above values.
In some embodiments, in step S20, the time of the crosslinking reaction is 1 to 10 hours. In the crosslinking reaction process, the crosslinking agent is used as a block framework to crosslink and modify the carbon source to expand the three-dimensional space, so that the carbon source forms a precursor with a three-dimensional structure, and the crosslinking agent contains carbon atoms and the carbon source contains carbon atoms which can be used as sources of the carbon atoms to form a three-dimensional structure with interconnected carbon atoms and hetero atoms. Specifically, the time of the crosslinking reaction may be 1h, 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h or within a range consisting of any of the above values.
In some embodiments, in step S20, the temperature of the crosslinking reaction is within ±70 ℃ of the boiling point of the crosslinking agent. In the temperature range of the crosslinking reaction, the crosslinking agent is in a gas-liquid two-phase balanced state, so that the uniform mixing of the crosslinking agent and the carbon source is facilitated, and the expansion of the carbon source to a three-dimensional space is realized.
In some embodiments, in step S30, the carbonization treatment comprises treating under a protective atmosphere at 650-1500 ℃ for 1-24 hours. In the carbonization treatment process, hetero atoms in the cross-linking agent can be uniformly doped into the three-dimensional porous framework, so that defect sites and interlayer spacing of hard carbon are further increased.
In some specific embodiments, the carbonization treatment temperature may be 650 ℃, 700 ℃, 800 ℃, 900 ℃, 1000 ℃, 1100 ℃, 1200 ℃, 1300 ℃, 1400 ℃, 1500 ℃, or within a range consisting of any of the above values. The carbonization treatment time may be 1h, 5h, 10h, 12h, 15h, 17h, 19h, 20h, 22h, 24h or within a range consisting of any of the above values.
In some embodiments, the protective atmosphere protects at least one of an argon atmosphere, a helium atmosphere, a neon atmosphere, a nitrogen atmosphere.
A third aspect of the embodiment of the present application provides a negative electrode, including a current collector and a negative electrode active material layer bonded to a surface of the current collector, wherein the negative electrode active material layer contains the negative electrode material of the present application or the negative electrode material prepared by the preparation method of the negative electrode material of the present application.
The negative electrode provided by the third aspect of the embodiment of the application has the advantages that the negative electrode material is provided with the three-dimensional framework structure formed by interconnecting carbon atoms and heteroatoms, so that the sodium storage performance, the multiplying power performance and the cycle stability of the negative electrode can be effectively improved, and the negative electrode material is safe to use and long in service life.
The fourth aspect of the embodiment of the application provides a secondary battery, which comprises a positive plate, a negative plate, a diaphragm and electrolyte, wherein the negative plate is the negative electrode of the application.
The secondary battery provided by the fourth aspect of the embodiment of the application has higher capacity, rate capability and cycle stability because of the negative electrode provided by the application.
In some embodiments, the secondary battery is a sodium ion battery having a first coulombic efficiency greater than 75% at a 0.2C rate, a first charge capacity greater than 250mAh/g, and a sloped region capacity greater than 150mAh/g.
The following description is made with reference to specific embodiments.
Example 1
The embodiment provides a negative electrode material and a preparation method thereof.
A negative electrode material comprising a hard carbon three-dimensional porous structure, the skeleton of which comprises a block skeleton containing phosphorus atoms and phosphorus atoms uniformly doped in the structure. The mass ratio of the phosphorus atoms in the anode material is 2.8wt%; the number of pores contained in the cathode material is 18.8%, the ratio of micropores is 75.7%, and the ratio of macropores is 5.5%.
A preparation method of a negative electrode material comprises the following steps:
step S1, respectively weighing 10g of phenolic resin, 0.5g of phosphoric acid and 5g of water according to the mass ratio of 100:5:50, uniformly mixing the weighed phenolic resin, phosphoric acid and water to obtain a mixed solution, evaporating the mixed solution to dryness under the condition of 80 ℃, and then carrying out crosslinking reaction for 3 hours under the condition of 260 ℃ under the nitrogen atmosphere to obtain a hard carbon precursor;
and S2, carbonizing the hard carbon precursor for 2 hours at the temperature of 1000 ℃ in a nitrogen atmosphere, and cooling to obtain the anode material.
Example 2
The embodiment provides a negative electrode material and a preparation method thereof.
A negative electrode material comprises hard carbon and phosphorus atoms distributed in the hard carbon, wherein the skeleton of the hard carbon three-dimensional porous structure comprises a block skeleton containing the phosphorus atoms and the phosphorus atoms uniformly doped in the structure. The mass ratio of the phosphorus atoms in the anode material is 0.7wt%; the cathode material contains 14.3% of micropores, 75.1% of mesopores and 5.0% of macropores.
A preparation method of a negative electrode material comprises the following steps:
step S1 is the same as step S1 in embodiment 1, except that: respectively weighing 10g of phenolic resin, 0.1g of phosphoric acid and 5g of water according to the mass ratio of 100:1:50;
step S2 is the same as step S2 in example 1.
Example 3
The embodiment provides a negative electrode material and a preparation method thereof.
A negative electrode material includes a hard carbon three-dimensional porous structure, the skeleton of which includes a block skeleton containing phosphorus atoms and phosphorus atoms uniformly doped in the structure. The mass ratio of the phosphorus atoms in the anode material is 7.49wt%; the number of pores contained in the cathode material is 26.6%, the ratio of micropores is 70.2%, and the ratio of macropores is 3.2%.
A preparation method of a negative electrode material comprises the following steps:
step S1 is the same as step S1 in embodiment 1, except that: respectively weighing 10g of phenolic resin, 2g of phosphoric acid and 5g of water according to the mass ratio of 100:20:50;
step S2 is the same as step S2 in example 1.
Example 4
The embodiment provides a negative electrode material and a preparation method thereof.
A negative electrode material comprising a hard carbon three-dimensional porous structure, the skeleton of which comprises a block skeleton of sulfur atoms and sulfur atoms uniformly doped in the structure. The mass ratio of sulfur atoms in the cathode material is 2.6wt%; the cathode material contains 20.7% of micropores, 74.2% of mesopores and 5.1% of macropores.
A preparation method of a negative electrode material comprises the following steps:
step S1 is the same as step S1 in example 2, except that: replacing phosphoric acid with sulfuric acid;
step S2 is the same as step S2 in example 1.
Example 5
The embodiment provides a negative electrode material and a preparation method thereof.
A negative electrode material comprising a hard carbon three-dimensional porous structure, the skeleton of which comprises a block skeleton containing oxygen atoms and oxygen atoms uniformly doped in the structure. The mass ratio of oxygen atoms in the cathode material is 5.2wt%; the number of pores contained in the anode material is 21.4%, the ratio of micropores is 74.5%, and the ratio of macropores is 4.1%.
A preparation method of a negative electrode material comprises the following steps:
step S1 is the same as step S1 in example 2, except that: replacing phosphoric acid with succinic acid;
step S2 is the same as step S2 in example 1.
Example 6
The embodiment provides a negative electrode material and a preparation method thereof.
A negative electrode material comprises a hard carbon three-dimensional porous structure, wherein the skeleton of the three-dimensional porous structure comprises a block skeleton containing oxygen atoms, sulfur atoms and nitrogen atoms, and the oxygen atoms, the sulfur atoms and the nitrogen atoms are uniformly doped in the structure. The mass ratio of oxygen atoms in the anode material is 3.3wt%, the mass ratio of sulfur atoms is 1.4wt%, and the mass ratio of nitrogen atoms is 3.2wt%; the number of pores contained in the cathode material is 30.7%, the ratio of micropores is 65.5%, and the ratio of macropores is 3.8%.
A preparation method of a negative electrode material comprises the following steps:
step S1 is the same as step S1 in example 3, except that: replacing phosphoric acid with 2, 4-diaminobenzene sulfonic acid;
step S2 is the same as step S2 in example 1.
Comparative example 1
This comparative example provides a negative electrode material and a method for producing the same.
A negative electrode material, the negative electrode material being hard carbon.
A preparation method of a negative electrode material comprises the following steps:
and S1, treating phenolic resin in a tube furnace at the temperature of 1000 ℃ for 2 hours under the nitrogen atmosphere, taking out the material after the tube furnace is naturally cooled, crushing, and naturally cooling to obtain the anode material.
Preparation of battery piece and assembly of battery
Negative electrode plate: the negative electrode materials, binder (polyvinylidene fluoride), and conductive agent (SP-Li) provided in examples 1 to 6 and comparative example 1 were mixed according to 90:5:5, mixing and ball milling to obtain negative electrode slurry, coating the negative electrode slurry on the surface of a copper foil, rolling, and vacuum drying at 110 ℃ overnight to obtain the negative electrode plate.
A counter electrode: sodium metal sheet.
A diaphragm: a20. Mu. MPP/PE/PP separator was used. (glass fiber film).
Sodium-electricity electrolyte: 1.0M NaPF6/EC: DEC=1:1Vol%.
Assembling the button cell:
and assembling the sodium ion battery in an inert atmosphere glove box according to the assembling sequence of the sodium metal sheet, the diaphragm, the electrolyte and the negative electrode sheet. The batteries including the negative electrode sheets of the negative electrode materials provided in examples 1 to 6 were respectively referred to as examples S1 to S6, and the batteries including the negative electrode material of comparative example 1 were referred to as comparative example DS1.
Performance testing
(1) Characterization of physical Properties
I D /I G The test method of (2) is as follows: and (3) adopting a Raman test, cutting a section of the pole piece containing the carbon-carbon hard carbon material by an ion polishing method, and then placing the section on a Raman spectrum test bench for testing after focusing. The test is carried out by selecting 200 μm-500 μm range, testing more than 200 points at equal intervals within the range, and testing each point within 1000cm -1 To 2000cm -1 Between them; at 1320cm -1 To 1370cm -1 The peak appearing therebetween is the D peak at 1570cm -1 To 1620cm -1 The peak appearing in the middle is G peak, the intensity ratio of ID/IG of each point is counted, and then the average value of a plurality of points is calculated as the final intensity ratio of ID/IG.
The d002 crystal face interlayer spacing testing method comprises the following steps: the negative electrode material was subjected to powder XRD test, and the test scan range was from 10 to 90 degrees at 2-fold scattering angle.
The method for testing the heteroatom content comprises the following steps: and (3) after platinum plating is carried out on the surface of the negative electrode material powder, placing the negative electrode material powder into a sample chamber of a scanning electron microscope, amplifying and observing a test position by using an accelerating voltage of 15kV, and carrying out element qualitative semi-quantitative analysis on the sample by using an X-ray energy spectrum analyzer.
The pore volume test method comprises the following steps: and obtaining the pore volume according to low-temperature nitrogen adsorption by adopting a gas adsorption method.
The specific surface area test method comprises the following steps: and a gas adsorption method is adopted, and the specific surface area is obtained according to low-temperature nitrogen adsorption.
(2) Characterization of results
The negative electrode material prepared in example 1 was subjected to scanning electron microscope analysis (SEM), and the results are shown in fig. 2. As can be seen from fig. 2, the anode material exhibits a three-dimensional skeleton structure, and a small amount of macroporous structure can be seen.
The negative electrode material prepared in example 1 was subjected to X-ray spectroscopy analysis (EDS), and the result is shown in fig. 3. As can be seen from fig. 3, the phosphorus atoms doped in the anode material are uniformly distributed in the three-dimensional skeleton.
The anode material prepared in example 1 was subjected to X-ray diffraction analysis (XRD), and the results are shown in fig. 4. As can be seen from fig. 4, the abscissa angle corresponding to the peak on the left side of the X-ray spectrogram is 22.84 °, which indicates that the anode material has a larger interlayer spacing.
(3) Electrochemical performance test
In an environment of 25 ℃, standing the assembled button cell for 8 hours, and then performing charge and discharge test, wherein the test flow is as follows: the button cell was charged and discharged at a rate of 0.2C (1c=300 mA/g). Gram capacity of first discharge and gram capacity of first charge were recorded, first coulombic efficiency = first charge capacity/first discharge capacity 100%; gram capacity and voltage in the charge and discharge process are recorded respectively, and gram capacity distribution in each voltage interval in the sodium removal process is counted. In the first run of the sodium removal curve, capacities of 0.1V to 1.5V were recorded.
The rate performance test method comprises the following steps: the button cell was charged and discharged at a rate of 10C, and the charge capacity of the 1 st turn was recorded.
The cycle life test method comprises the following steps: the button cell was charged and discharged at a rate of 5C, and the capacities of the 2 nd and 2000 th turns were recorded in 2000 turns, and the cycle life=2000 th turn charge capacity/second turn discharge capacity was 100%.
(3) Test results
The test results are shown in tables 1 to 2.
Table 1 test results
TABLE 2 electrochemical Performance test results
According to table 1, the introduction of the cross-linking agent enables hetero atoms to be embedded in the carbon skeleton, and the content of the cross-linking agent and the three-dimensional skeleton structure of the formed porous multilevel can be properly adjusted according to the addition amount, so that the pore volume, the specific surface area, the disorder degree and the interplanar spacing of the anode material are adjusted and controlled; more specifically, in examples S1 to S3, the doped hetero atom is P, and the content of P atoms in the three-dimensional structure is adjusted by adjusting the dosage of the cross-linking agent, and meanwhile, the increase of the content of P atoms is positively correlated with the increase of the specific surface area and the pore volume. By combining examples S1 to S6 and comparative example DS1 of tables 1 and 2, it can be seen that the three-dimensional skeleton structure imparts abundant defects and active centers to the anode material, exhibits a large charge ramp capacity in the interval of 0.1 to 0.5V, has high first coulomb efficiency, greatly increases the overall reversible capacity, and has excellent sodium storage performance. In addition, the doping of the hetero atoms in the framework can be used for controllably adjusting the pore structure, so that the sodium ion transmission path and the electron conduction diffusion path are effectively shortened, and the anode material still shows excellent rate performance and ultra-long cycle life under 10C high current, which is far more than that of comparative example DS1.
The foregoing description of the preferred embodiments of the application is not intended to be limiting, but rather is intended to cover all modifications, equivalents, and alternatives falling within the spirit and principles of the application.
Claims (11)
1. A negative electrode material characterized by comprising a hard carbon three-dimensional porous structure, wherein at least part of the skeleton of the hard carbon three-dimensional porous structure is a block skeleton containing hetero atoms.
2. The anode material according to claim 1, wherein the skeleton of the hard carbon three-dimensional porous structure is uniformly doped with hetero atoms.
3. The anode material according to any one of claims 1 to 2, wherein the heteroatom comprises at least one of N, O, S, P, B, F;
the hetero atom accounts for 0.01-15 wt% of the total mass of the anode material.
4. The anode material of claim 1, wherein the hard carbon three-dimensional porous structure comprises interconnected multi-stage mesh.
5. The anode material of claim 4, wherein the multi-stage mesh comprises micropores, mesopores, and macropores.
6. The negative electrode material according to claim 5, wherein the micropores account for 10 to 40% of the number of pores contained in the negative electrode material; and/or
The mesoporous accounts for 40-80% of the number of pores contained in the anode material; and/or
The macropores account for 1-15% of the number of the pores contained in the anode material.
7. The anode material according to any one of claims 1 to 6, wherein the anode material has a primary particle diameter of 50 to 700nm and a secondary particle diameter of 0.5 to 100 μm; and/or
The pore volume of the anode material is 0.01-0.8 cm 3 /g; and/or
The specific surface area of the negative electrode material is 0.5-1000 m 2 /g; and/or
D of the negative electrode material 002 The interlayer spacing of the crystal face is 0.370-0.410 nm; and/or
Peak intensity I of D-band of the negative electrode material D Peak intensity I with G band G The ratio of the two is 0.8-1.9.
8. The preparation method of the anode material is characterized by comprising the following steps of:
providing a carbon source and a heteroatom-containing crosslinking agent;
dispersing the carbon source and the crosslinking agent into a solvent, and performing a crosslinking reaction after desolvation treatment to obtain a hard carbon precursor with a three-dimensional structure;
and carbonizing the hard carbon precursor to obtain the anode material.
9. The method for producing a negative electrode material according to claim 8, wherein a mass ratio of the carbon source, the crosslinking agent, and the solvent is 100:0.01 to 20:50 to 200; and/or
The hetero atom in the cross-linking agent comprises at least one of nitrogen element, oxygen element, sulfur element, phosphorus element, boron element and fluorine element; and/or
The time of the crosslinking reaction is 1-10 h; and/or
The carbonization treatment comprises the treatment for 1 to 24 hours under the condition of 650 to 1500 ℃ in a protective atmosphere.
10. A negative electrode comprising a current collector and a negative electrode active material layer bonded to the surface of the current collector, wherein the negative electrode active material layer contains the negative electrode material according to any one of claims 1 to 7 or the negative electrode material produced by the method for producing a negative electrode material according to any one of claims 8 to 9.
11. A secondary battery comprising a positive electrode sheet, a negative electrode sheet, a separator, and an electrolyte, wherein the negative electrode sheet is the negative electrode of claim 10.
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| CN117423835B (en) * | 2023-12-19 | 2024-04-02 | 溧阳中科海钠科技有限责任公司 | Negative electrode material and sodium ion battery |
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