CN116470048A - Positive electrode lithium supplementing agent, preparation method and application thereof - Google Patents
Positive electrode lithium supplementing agent, preparation method and application thereof Download PDFInfo
- Publication number
- CN116470048A CN116470048A CN202210031227.7A CN202210031227A CN116470048A CN 116470048 A CN116470048 A CN 116470048A CN 202210031227 A CN202210031227 A CN 202210031227A CN 116470048 A CN116470048 A CN 116470048A
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- China
- Prior art keywords
- positive electrode
- lithium
- agent
- battery
- supplementing agent
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 215
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 199
- 230000001502 supplementing effect Effects 0.000 title claims abstract description 134
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 140
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- 239000000126 substance Substances 0.000 claims abstract description 36
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- 239000010410 layer Substances 0.000 claims description 42
- 238000000498 ball milling Methods 0.000 claims description 40
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- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B19/00—Selenium; Tellurium; Compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B19/00—Selenium; Tellurium; Compounds thereof
- C01B19/002—Compounds containing, besides selenium or tellurium, more than one other element, with -O- and -OH not being considered as anions
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
-
- 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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The embodiment of the application provides a positive electrode lithium supplementing agent, which comprises a particle body, wherein the particle body comprises a lithium compound of a sulfur selenide of a transition metal, and the average chemical formula of the lithium compound of the sulfur selenide of the transition metal is Li x MS y Se 2‑y Wherein x is more than 1 and less than or equal to 4, y is more than 0 and less than 2, and M represents transition metal. The positive electrode lithium supplementing agent has low decomposition voltage when the active lithium ions are removed, does not generate gas, can provide high lithium supplementing capacity, and the product after lithium removal does not influence the exertion of the positive electrode performance of the battery. The embodiment of the application also provides a preparation method of the positive electrode lithium supplementing agent, a battery positive electrode plate, an electrochemical battery and electronic equipment.
Description
Technical Field
The embodiment of the application relates to the technical field of batteries, in particular to a positive electrode lithium supplementing agent, a preparation method and application thereof.
Background
With the development of economy and science, the industries of portable electronic devices (mobile phones, tablet computers, notebook computers, etc.), unmanned aerial vehicles, electric vehicles, etc. all have urgent demands for energy storage devices with higher energy density and longer cycle life. In order to make the energy storage device of the lithium ion battery meet the above requirements, a common measure adopted in the industry is to add a lithium supplementing agent capable of providing active lithium into the lithium ion battery system in advance so as to compensate the irreversible loss of the negative electrode to the active lithium in the first charging process of the battery.
At present, the scheme of supplementing lithium to the battery can be mainly divided into positive electrode lithium supplementing and negative electrode lithium supplementing. The potential safety hazard of the cathode lithium supplementing material is large, and the cathode lithium supplementing material is difficult to be compatible with the preparation process of the cathode plate, thereby preventing the commercial application of the cathode lithium supplementing material. However, the common positive electrode lithium supplementing material is generally compatible with the preparation process of the positive electrode plate, but still cannot meet the requirements of high lithium supplementing capacity, low gas production, low residual side effect and the like.
Disclosure of Invention
In view of this, the embodiment of the application provides a positive electrode lithium supplementing agent, which has low lithium removal and decomposition voltage, high lithium supplementing capacity, no gas generation when active lithium ions are removed, and high ionic conductivity of a lithium removal product, and does not influence the exertion of the positive electrode performance of a battery.
Specifically, a first aspect of the embodiments of the present application provides a positive electrode lithium-supplementing agent, which includes a particle body including a lithium compound of a sulfur selenide of a transition metal, wherein the average chemical formula of the lithium compound of the sulfur selenide of the transition metal is Li x MS y Se 2-y Wherein x is more than 1 and less than or equal to 4, y is more than 0 and less than 2, and M represents transition metal.
The positive electrode lithium supplementing agent has good conductivity, low lithium removal decomposition voltage, and can decompose and generate more active lithium ions in the battery core formation stage (namely, the actual lithium supplementing capacity is high), so that the irreversible consumption of the negative electrode to the active lithium in the primary charging process of the battery can be supplemented, and the energy density and the cycle performance of the battery can be improved; in addition, the lithium is removed without generating gas, the ionic conductivity of the solid residue after the lithium removal is high, the impedance of the battery core is not increased, and the multiplying power performance of the battery is not affected. Therefore, the positive electrode lithium supplementing agent can supplement active lithium loss for the battery under the condition of not affecting other performances of the battery, and the energy density of the battery is better improved.
In an embodiment of the present application, the particle body comprises a particle of the general formula Li x MS y Se 2-y Is a compound of (2) and M, li 2 S and Li 2 Se. Therein, M, li 2 S and Li 2 Se can be obtained by the compound Li x MS y Se 2-y And partially decomposing to obtain the final product. M, li different from simple mixing 2 S and Li 2 Se, which are closely combined in the positive electrode lithium supplementing agent, such as nano-scale contact, can release lithium ions in the cell formation stage to be converted into sulfur selenium compounds of transition metals, avoiding M, li like simple mixing 2 S and Li 2 Li in Se mixture 2 S is decomposed to produce gas.
In some embodiments of the present application, the particle body further comprises a particle of the formula LiMS y Se 2-y Is a compound of (a). LiMS (LiMS) y Se 2-y Is very stable in structure.
In embodiments of the present application, M may include one or more of Cr, ti, V, co, fe, ni, mn, nb.
In an embodiment of the present application, the surface of the particle body further has a coating layer. The existence of the coating layer can endow the positive electrode lithium supplementing agent with good air stability and processability.
The second aspect of the embodiment of the application also provides a preparation method of the positive electrode lithium supplementing agent, which comprises the following steps:
mixing a transition metal source, a sulfur source and a selenium source, ball milling and sintering to prepare a sulfur selenide of the transition metal;
Lithiation is carried out on the sulfur selenium compound of the transition metal to obtain a positive electrode lithium supplementing agent; wherein the positive electrode lithium supplementing agent comprises a particle body, the particle body comprises a lithium compound of a sulfur selenide of a transition metal, and the average chemical formula of the lithium compound of the sulfur selenide of the transition metal is Li x MS y Se 2-y Wherein x is more than 1 and less than or equal to 4, y is more than 0 and less than 2, and M represents transition metal.
The preparation method of the positive electrode lithium supplementing agent provided in the second aspect of the embodiment of the application is simple in process, efficient and environment-friendly, and can be used for large-scale production.
The third aspect of the embodiment of the application also provides a battery positive electrode plate, which contains the positive electrode lithium supplementing agent according to the first aspect of the embodiment of the application. The electrode plate containing the positive electrode lithium supplementing agent can be used for providing an electrochemical cell with high energy density and long cycle life.
In some embodiments of the present application, the battery positive electrode sheet includes a current collector and a positive electrode material layer disposed on the current collector, the positive electrode material layer including a positive electrode active material, a positive electrode lithium supplement agent according to the first aspect of the embodiment of the present application, and a binder. In the manufacturing process of the battery positive electrode plate, the introduction of the positive electrode lithium supplementing agent can not cause jelly formation of positive electrode slurry for forming a positive electrode material layer, and the positive electrode material layer is easy to coat and obtain a film layer with high flatness.
In some embodiments of the present application, the battery positive electrode sheet includes a current collector, and a positive electrode material layer and a lithium supplementing agent layer sequentially disposed on the current collector, wherein the positive electrode material layer contains a positive electrode active material, a binder and a conductive agent, and the lithium supplementing agent layer contains the positive electrode lithium supplementing agent, the binder and the conductive agent.
The fourth aspect of the embodiment of the application also provides an electrochemical cell, which comprises a positive electrode, a negative electrode, a separator and electrolyte, wherein the separator and the electrolyte are positioned between the positive electrode and the negative electrode, and the positive electrode is the positive electrode plate of the cell in the third aspect of the embodiment of the application. The electrochemical cell has a high energy density and a long cycle life.
A fifth aspect of the embodiments of the present application also provides an electronic device comprising an electrochemical cell according to the fourth aspect of the embodiments of the present application.
The electronic device can be various consumer electronic products, such as mobile phones, tablet computers, notebook computers, intelligent wearing products and the like, and can also be a mobile device, such as an electric automobile.
Drawings
Fig. 1 is a schematic view of one construction of an electrochemical cell provided in an embodiment of the present application.
Fig. 2 is a schematic structural diagram of a positive electrode tab of a battery according to an embodiment of the present application.
Fig. 3 is a schematic structural view of a positive electrode tab of a battery according to another embodiment of the present application.
Fig. 4 is a schematic structural diagram of an electronic device according to an embodiment of the present application.
Fig. 5 is a schematic structural diagram of another electronic device according to an embodiment of the present application.
FIG. 6 is a positive electrode lithium-supplementing agent Li in example 1 of the present application x The results are characterized by an X-ray diffraction (XRD) of CrSSe and its precursor CrSSe.
Fig. 7 is a first-turn charge-discharge curve of the half cell of example 1 of the present application.
Fig. 8 is a first-turn charge-discharge curve of the half cell of comparative example 1.
Fig. 9 is a comparative example 2 half cell (i.e., pure LiFePO 4 Button cell) is provided.
Fig. 10 is a schematic diagram of a half cell of example 2 (LiFePO 4 Button cell mixed with positive electrode lithium supplement).
Detailed Description
Embodiments of the present application are described below with reference to the accompanying drawings in the embodiments of the present application.
As shown in fig. 1, fig. 1 is a schematic structural view of an electrochemical cell 100 provided in an embodiment of the present application, and the electrochemical cell 100 may be a lithium secondary battery. The lithium secondary battery includes a positive electrode 101, a negative electrode 102, a separator 103, an electrolyte 104, and corresponding communication auxiliaries and circuits. The positive electrode 101 and the negative electrode 102 can store and release energy by extracting active metal ions (lithium ions are active metal ions for lithium secondary batteries): active metal ions are separated from the positive electrode under the drive of an external circuit and migrate to the negative electrode through the electrolyte 104 and the diaphragm 103, so that the battery is charged; when an external power load is used, active metal ions are separated from the negative electrode and migrate back to the positive electrode, and a discharging process is carried out.
All active lithium in a lithium ion battery is provided by the positive electrode material. However, active lithium ions are consumed by the formation of a solid electrolyte film (solid electrolyte interphase, SEI film) on the surface of the negative electrode during the first charge of a lithium ion battery and other chemical side reactions during subsequent charge-discharge cycles, resulting in a loss of reversible capacity and a reduction in energy density of the battery. In order to increase the energy density of a lithium ion battery, a solution commonly used in the industry is to add a lithium supplementing agent to the positive electrode of the battery, and the commonly used positive electrode lithium supplementing agent generally comprises a binary lithium compound, a ternary lithium compound, or an organic lithium salt. Wherein Li is 2 NiO 2 、Li 6 CoO 4 The theoretical lithium supplementing capacity of the ternary lithium-containing compound is low, and the ionic and electronic conductivity of the residue after lithium supplementation is poor, so that the performance of the battery multiplying power is not facilitated. While lithium oxalate (Li) 2 C 2 O 4 )、Li 2 C 3 O 5 The theoretical specific capacity of the organic lithium salt is moderate, but the prominent disadvantage of the organic lithium salt is high decomposition voltage and limited practical lithium supplementing capacity. Li (Li) 2 O、LiF、Li 2 S、Li 3 Although the theoretical specific capacity of binary lithium-containing compounds such as N is high, the decomposition voltage is also high due to the poor electron conductivity of the compounds themselves, and the gas generated by the decomposition of the compounds affects the cycle performance and safety performance of the battery. In view of this, the embodiments of the present application provide a positive electrode lithium-supplementing agent that can achieve good conductivity, low decomposition voltage, high lithium-supplementing capacity, no gas generation during delithiation, and the like.
Specifically, the positive electrode lithium supplementing agent provided by the embodiment of the application comprises a particle body, wherein the particle body comprises a lithium compound of a sulfur selenide of a transition metal, and the sulfur selenide of the transition metalThe average chemical formula of the lithium compound of the compound is Li x MS y Se 2-y Wherein x is more than 1 and less than or equal to 4, y is more than 0 and less than 2, and M represents transition metal.
The positive electrode lithium supplementing agent has good conductivity, low lithium removal decomposition voltage, and can decompose and generate more active lithium ions (namely, high actual lithium supplementing capacity) in the battery core formation stage, supplement irreversible consumption of the negative electrode to the active lithium in the first charging process of the battery, and be favorable for improving the energy density and the cycle performance of the battery. In addition, the lithium removal reaction formula of the positive electrode lithium supplementing agent is as follows: li (Li) x MS y Se 2-y -e - →MS y Se 2-y +xLi + . The lithium supplementing agent does not generate gas during the lithium removal, so that various gas generation problems are avoided (such as the need of increasing the volume of an exhaust bag in the battery manufacturing process and the problem that the gas generated by the lithium removal of the common positive electrode lithium supplementing agent is partially dissolved in electrolyte to increase the side reaction degree of the electrolyte) are avoided, and the residue after the removal of active lithium is mainly the sulfur selenium compound MS of transition metal y Se 2-y The ionic conductivity is high, the impedance of the battery core is not increased, the multiplying power performance of the battery is not affected, and the gas production risk of the electrolyte is not increased. Therefore, the positive electrode lithium supplementing agent can supplement active lithium loss for the battery under the condition of not affecting other performances of the battery, and the energy density of the battery is better improved.
In the present application, the molar ratio of Li element to M element in the particle body is in the range of more than 1 to 4. That is, the value range of x is: x is more than 1 and less than or equal to 4. At this time, the lithium supplementing capacity of the particle body of the positive electrode lithium supplementing agent is high. In some embodiments, x may be 2, 2.5, 3, 3.5, 4, or the like. In some embodiments of the present application, y may be 0.2, 0.5, 1, 1.5, 1.8, etc.
In this application, the particle body may be obtained by lithiation of a sulfur selenide of a transition metal. In some embodiments of the present application, the particle body comprises a polymer of the general formula Li x MS y Se 2-y Is a compound of (a).
In some embodiments of the present application, the particle body comprises a polymer of the general formula Li x MS y Se 2-y Is a compound of (2) and M, li 2 S and Li 2 Se. Therein, M, li 2 S and Li 2 Se can pass through Li x MS y Se 2-y And partially decomposing to obtain the final product. In the present application, regardless of Li x MS y Se 2-y Partially decomposed or not, the average chemical formula of the particle body is Li x MS y Se 2-y 。
M, li different from simple mixing 2 S and Li 2 Se, in which these substances in the positive electrode lithium-supplementing agent are tightly bound, e.g. nano-scale contacts, M, li 2 S and Li 2 Se can be used for removing lithium ions in the cell formation stage to be converted into a sulfur selenium compound of transition metal, and the lithium removal reaction formula is as follows: M+Li 2 Se+Li 2 S-4e - →MS y Se 2-y +4Li + . It can be seen that even Li x MS y Se 2-y Certain decomposition occurs, and the decomposition products can still jointly undergo lithium removal reaction without generating gas, thereby avoiding Li-like reaction 2 S, or M, li of simple physical mixing 2 S and Li 2 Li in mixture of Se 2 S generates the phenomenon of decomposing and generating gas, correspondingly, li is avoided 2 SO produced by S decomposition 2 And the gas influences the circulation and the safety performance of the battery.
In some embodiments of the present application, the particle body further comprises a particle of the formula LiMS y Se 2-y Is a compound of (a). LiMS compound y Se 2-y The structure stability of the lithium ion battery is very high, and a certain lithium supplementing capacity can be contributed. At this time, the particle body includes a material having the general formula Li x MS y Se 2-y Compound (x.noteq.1) of (a) and M, li) 2 S and Li 2 Se, also the compound LiMS y Se 2-y . Wherein, the compound LiMS y Se 2-y By Li x MS y Se 2-y Is converted from the compound (x.noteq.1).
In the present application, M is selected from transition metal elements. In the embodiment of the present application, M may include one or more of chromium Cr, titanium Ti, vanadium V, cobalt Co, iron Fe, nickel Ni, manganese Mn, niobium Nb, but is not limited thereto. In the present application, when the expression "plurality" is referred to, the expression "plurality" means two or more.
In some embodiments of the present application, the surface of the particle body further has a doped layer. The doped layer may comprise the material of the particle body, except that a doping element is introduced therein. The doped layer may contain, for example, li containing a doping element x MS y Se 2-y A compound. Wherein the doping element can be a nonmetallic element, such as one or more of nitrogen N, phosphorus P, carbon C and boron B; but may also be a transition metal element/metal element other than M, such as one or more of molybdenum Mo, tungsten W, zirconium Zr, silver Ag, copper Cu, tin Sn, antimony Sb, aluminum Al, magnesium Mg, calcium Ca, and the like; of course, co-doping of the two types of elements is also possible. The presence of doping elements can further promote the compound Li x MS y Se 2-y The structural stability of the anode material is ensured, and the anode material is favorable for being smoothly added into an anode system. In some embodiments, the doping element is preferably a nonmetallic element as described above.
In some embodiments of the present application, the surface of the particle body further has a coating layer. The material of the coating layer can be a material with ionic conductivity, so that the release of active lithium in the subsequent particle body is not affected. In some embodiments, the surface of the particle body may include the doped layer and the coating layer sequentially. Specifically, the material of the coating layer may include at least one of an inorganic carbon material, an organic polymer, an inert oxide, and the like. The coating layer material has good stability in air, is not easy to absorb water or oxygen, and the like, has low alkalinity, the positive electrode lithium supplementing agent with the coating layer can have good air stability and processability, and after the particle body of the positive electrode lithium supplementing agent is delithiated, the residual coating layer material can not increase the gas production risk of the battery electrolyte.
Specifically, as the inorganic carbon material, one or more of graphite, graphene, carbon nanotubes, carbon fibers, carbon black, pyrolytic carbon, and the like may be cited, but is not limited thereto. Examples of the organic polymer include a polyacrylate such as parylene and a derivative thereof, polymethyl methacrylate (PMMA), a polyolefin such as Polyethylene (PE) and polystyrene; as the inert oxide, silica, oxides of the metal elements of the first to third main groups (such as alumina, magnesia, barium oxide, etc.), non-catalytically active transition metal oxides (such as titania, zinc oxide, zirconia, tin oxide, etc.), etc. can be cited. Wherein, when the coating layer is made of inorganic carbon material, the conductivity of the positive electrode lithium supplementing agent can be improved. Most of the coating layers can be formed by mixing the raw materials of the coating layer material with a positive electrode lithium supplementing agent and then performing heat treatment.
In embodiments of the present application, the thickness of the coating layer may be in the range of 3nm to 1000nm, for example, may be in the range of 5nm to 500 nm. The thickness of the coating layer can be adjusted according to the size of the positive electrode lithium supplementing agent, and the proper thickness of the coating layer can ensure that the positive electrode lithium supplementing agent has good processing performance, and can avoid the influence of excessive thickness on the timely release of active lithium and increase the impedance of a battery.
In some embodiments of the present application, the mass of the coating layer may account for 0.01wt% to 10wt% of the mass of the positive electrode lithium-compensating agent. The lower mass ratio enables the coating layer to have better air stability and processability in improving the anode lithium supplementing agent, and the lithium supplementing specific capacity of the whole material is reduced too much.
The actual lithium supplementing capacity of the positive electrode lithium supplementing agent provided by the embodiment of the application is high, no gas is produced during lithium removal, the play of the positive electrode performance of the battery is not influenced by residues after lithium removal, and the energy density, the cycle performance and the like of the battery can be well improved.
Correspondingly, the embodiment of the application also provides a preparation method of the positive electrode lithium supplementing agent, and the preparation method is simple in process, easy to operate, efficient, environment-friendly and capable of realizing large-scale production. The preparation method specifically comprises the following steps:
s01, ball milling a transition metal source, a sulfur source and a selenium source to obtain a mixture, and sintering the mixture to obtain a sulfur selenide of the transition metal;
s02, lithiating the sulfur selenium compound of the transition metal to obtain a positive electrode lithium supplementing agent; wherein the positive electrode lithium supplementing agent comprises a particle body, and the particle bodyThe body comprises a lithium compound of a sulfur selenide of a transition metal, and the average chemical formula of the lithium compound of the sulfur selenide of the transition metal is Li x MS y Se 2-y Wherein x is more than 1 and less than or equal to 4, y is more than 0 and less than 2, and M represents transition metal.
In step S01, the transition metal source may be one or more of simple substance, oxide, hydroxide, salt, etc. of transition metal; the sulfur source may be S and alkali metal sulfide (such as Li 2 S、Na 2 S、K 2 S) one or more of; the selenium source can be Se, li 2 Se、Na 2 Se、K 2 One or more of Se. In some embodiments of the present application, at least one of the sulfur source and the selenium source includes a corresponding compound of an alkali metal, such that a precursor of the lithium-compensating agent is more readily available.
The preparation of the mixture can be obtained by ball milling after mixing a transition metal source, a sulfur source and a selenium source. Wherein, the rotation speed of ball milling can be 400-1600r/min, and can be 500, 800, 1000, 1200 or 1500r/min. The higher ball milling rotation speed is favorable for lattice reconstruction among the raw materials, and is convenient for sintering to obtain the precursor-transition metal sulfur selenium compound for forming the lithium supplementing agent. In some embodiments, the rotational speed of the ball mill may be 800-1500r/min. Wherein the ball milling time can be 5min-300min, specifically 20min, 30min, 60min, 120min, 180min, 200min, 240min, etc. In addition, the ball-to-material ratio during ball milling may be in the range of (1-30): 1. Higher ball-to-material ratios may better achieve lattice reconstruction.
Wherein, the sintering treatment can help the ball milling mixture to grow again, eliminate lattice defects and the like. Wherein the sintering temperature can be 700-1000 ℃, and can be 750, 800, 850, 900 or 950 ℃ and the like. The heat preservation time in sintering can be 8-24 h, and can be specifically 10, 12, 16, 18 or 20h, etc. The sintering process may be performed under an inert atmosphere, which may be argon, helium, or the like. Further, since the temperature rising rate is too fast, a large stress is generated on the interface between the phases, the temperature rising rate is controlled to be 1-5 ℃/min in the sintering treatment process.
In some embodiments of the present application, the above mixture is obtained by ball milling after mixing a transition metal simple substance, a sulfur simple substance, an alkali metal sulfide and a selenium simple substance. Further, when the alkali metal in the alkali metal sulfide is not lithium (M' is not Li), it further includes, after sintering: and adopting iodine simple substance to make displacement reaction so as to obtain the sulfur selenium compound of transition metal. The reaction equation involved is:
1)M’ 2 S+(2y-1)S+2(2-y)Se+2M＝＝2M’MS y Se 2-y ；
2)2M’MS y Se 2-y +I 2 ＝＝2MS y Se 2-y +2M’I；
m' represents an alkali metal element. Unreacted elemental iodine can be washed away by solvents such as acetonitrile, acetone, and the like.
In step S02, the lithiation mode includes one or more of electrochemical lithiation, organic lithiation reagent lithiation, metal lithiation, and the like. The electrochemical lithiation is generally to place a material to be lithiated and a lithium source in an electrolyte after tabletting, and the material to be lithiated and the lithium source are separated by a diaphragm, and the material to be lithiated and the diaphragm are electrically connected through an external circuit, so that lithium supplementing of the material to be lithiated can be realized during electrifying. The lithium source is typically a self-supporting lithium plate, a lithium-plated metal sheet, or a lithium foil attached to other thin film substrates. The lithiation is performed by using an organic lithiation reagent, specifically, a material to be lithiated is placed in the organic lithiation reagent, lithium ions in the organic lithiation reagent are extracted and are inserted into the material to be lithiated, so that the lithiation is realized. The organic lithiation reagent is generally an aryl lithiation reagent, and specifically may be one or more of naphthalene lithium, anthracene lithium, phenanthrene lithium, biphenyl lithium, and the like. The metal lithium used for lithiation may be one or more of lithium powder, lithium foil, molten lithium liquid, and the like. The lithium powder and the lithium foil are generally pressed together with the material to be lithiated, and the molten lithium liquid is generally mixed with (e.g., cast onto) the material to be lithiated to achieve the lithiation of the latter. Wherein, adjusting parameters (such as lithiation time and the like) in the lithiation process can realize the regulation and control of the subscript x in the particle body of the lithium supplementing agent.
In some embodiments of the present application, the resulting particle bodies may also be subjected to some post-treatment, such as doping, surface coating, etc., after the above-described lithiation. Wherein doping, surface cladding generally involves heat treatment. Examples of surface coating of the particle body are as follows. After the above step S02, the following step S03 is included.
S03, mixing the particle body with the coating layer raw material to form a coating layer on the surface of the particle body.
Wherein, the raw materials of the coating layer can be directly selected as the raw materials of the coating layer, or can be selected as the raw materials of the synthetic coating layer. If the raw materials are selected to be synthesized coating materials, a precursor of the coating materials is generally formed on the surface of the particle body of the positive electrode lithium supplementing agent, and further heat treatment is needed to promote the precursor to be converted into the coating materials and improve the binding force with the particle body. The coating layer is formed by one or more of ball milling, mechanical stirring, mechanical fusion, coating, spray drying, vapor deposition, thermal decomposition, etc. The coating mode can specifically comprise one or a combination of a plurality of modes of dripping, brushing, spraying, dipping, scraping and spin coating. The vapor deposition method includes physical vapor deposition (such as vapor deposition, magnetron sputtering, vacuum thermal deposition, etc.), chemical vapor deposition, atomic layer deposition, etc. The method of constructing the coating layer may be selected according to the specific material.
The coating material is as described hereinbefore. Wherein, the inorganic carbon materials such as graphite, carbon nano tube, carbon fiber and the like are suitable for being coated by a ball milling method, and can be subjected to proper heat treatment after ball milling. The coating layer made of pyrolytic carbon is particularly suitable for construction by a thermal decomposition method, and specifically, an organic carbon source and a positive electrode lithium supplementing agent can be mixed (for example, ground or introduced with a gaseous carbon source) and then subjected to heat treatment, so that the organic carbon source is thermally decomposed into an inorganic conductive carbon layer. The organic polymer can be coated by a coating method, a spray drying method and the like, and part of the organic polymer (such as parylene and derivatives thereof) is more suitable for constructing a coating layer with high compactness and good application property by a chemical vapor deposition mode. The inert oxide may be coated by a coating method, a spray drying method, a vapor deposition method, or the like.
The embodiment of the application also provides a battery positive plate, which contains the positive electrode lithium supplementing agent. The positive electrode plate of the battery can be shown in fig. 2 or fig. 3.
In some embodiments of the present application, referring to fig. 2, the battery positive electrode tab 101 includes a current collector 1011 and a positive electrode material layer 1012 'disposed on the current collector 1011, the positive electrode material layer 1012' including a positive electrode active material, the positive electrode lithium-supplementing agent described in the examples of the present application, and a binder. In some embodiments, a conductive agent is also included in the positive electrode material layer 1012'. The positive electrode sheet shown in fig. 2 may be formed by coating a positive electrode slurry containing the above positive electrode lithium-supplementing agent, positive electrode active material, binder, and optional conductive agent on the current collector 1011, followed by drying and pressing.
Wherein the mass ratio of the positive electrode lithium-supplementing agent to the sum of the mass of the positive electrode lithium-supplementing agent and the mass of the positive electrode active material may be 1% -10%. The proper mass ratio of the positive electrode lithium supplementing agent can provide enough active lithium for the positive electrode plate without reducing the specific capacity of the positive electrode plate, thereby effectively improving the energy density of the battery. In some embodiments, the mass ratio may specifically be 2%, 3%, 5%, 7.5%, 9%, etc.
In the positive electrode sheet shown in fig. 2, the mass of the positive electrode lithium supplementing agent accounts for 0.5% -15% of the mass of the positive electrode material layer 1012'. The mass ratio can ensure that the battery prepared by the battery positive electrode plate 101 has higher capacity in the processes of primary charge and discharge and multiple non-primary charge and discharge, thereby leading the battery to have higher energy density and longer cycle life. In some embodiments, the mass ratio may be 2% -10%, and further may be 5% -10%. Wherein the mass of the binder may be 0.5% -10% of the mass of the positive electrode material layer 1012'. The mass of the conductive agent may be 0.5% -10% of the mass of the positive electrode material layer 1012'.
In other embodiments of the present application, referring to fig. 3, the positive electrode sheet 101 of the battery includes a current collector 1011, and a positive electrode material layer 1012 and a lithium supplementing agent layer 1013 sequentially disposed on the current collector 1011, wherein the positive electrode material layer 1012 contains a positive electrode active material, a binder and a conductive agent, and the lithium supplementing agent layer 1013 contains the positive electrode lithium supplementing agent, the binder and the conductive agent described in the embodiments of the present application.
The positive electrode sheet shown in fig. 3 can be produced by the steps of: the current collector 1011 is coated with a conventional positive electrode slurry, dried to form a positive electrode material layer 1012, and the positive electrode material layer 1012 is coated with a slurry containing a positive electrode lithium supplementing agent, an electric agent and a binder, and dried to obtain a lithium supplementing agent layer 1013. It will also be appreciated that this embodiment provides a positive electrode sheet that corresponds to the prior art positive electrode sheet plus the lithium supplement layer 1013 on its surface. As described above, in the positive electrode sheet shown in fig. 3, the mass ratio of the positive electrode lithium-compensating agent to the sum of the mass of the positive electrode lithium-compensating agent and the mass of the positive electrode active material may be 1% to 10%.
The current collector 1011 may be referred to as a positive electrode current collector, and includes, but is not limited to, a metal foil, an alloy foil, or a metal plating film, and the surface thereof may be etched or roughened to form a secondary structure, so as to be in effective contact with the positive electrode material layer. Exemplary metal foils may be aluminum foil, carbon coated aluminum foil, or aluminized film, and exemplary alloy foils may be stainless steel foil, aluminum alloy foil, or carbon coated stainless steel foil.
The positive electrode active material, the binder, and the conductive agent may be conventional choices in the field of batteries. Among them, the positive electrode active material may include, but is not limited to, at least one of lithium iron phosphate, lithium manganese iron phosphate, lithium vanadium phosphate, lithium cobalt oxide, lithium manganate, lithium nickel manganate, nickel Cobalt Manganese (NCM), nickel Cobalt Aluminum (NCA), and the like. The binder may specifically include, but is not limited to, one or more of Polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), polyvinyl alcohol (PVA), polyacrylic acid (PAA), polyacrylate, styrene-butadiene rubber (SBR), sodium carboxymethyl cellulose (CMC), sodium alginate, and the like. The conductive agent may specifically include, but is not limited to, one or more of acetylene black, ketjen black, provider P conductive carbon black, graphite, graphene, carbon nanotubes, carbon fibers, amorphous carbon, and the like.
In the battery positive electrode plate provided by the embodiment of the application, due to the fact that the positive electrode lithium supplementing agent is provided, the positive electrode plate can be used for providing an electrochemical battery with high energy density and long cycle life.
The embodiment of the application also provides an electrochemical cell, which comprises the positive electrode plate of the cell. The structure of the electrochemical cell may be as described in fig. 1 above. The electrochemical cell may be a secondary battery having high cycle performance and high safety. Specifically, the secondary battery may be a lithium secondary battery.
Wherein the anode 102 may include an anode current collector and an anode material layer disposed on the anode current collector, the anode material layer including an anode active material, a binder, and optionally a conductive agent. The negative electrode current collector comprises, but is not limited to, a metal foil, an alloy foil or a metal plating film, and the surface of the negative electrode current collector can be etched or roughened to form a secondary structure so as to be in effective contact with the negative electrode material layer. Exemplary metal foils may be copper foil, carbon coated copper foil, or copper coated film, and exemplary alloy foils may be stainless steel foil, copper alloy foil, and the like. The negative active material includes, but is not limited to, one or more of lithium titanate, metallic lithium (lithium simple substance or lithium alloy), carbon-based material, silicon-based material, tin-based material, and the like. Wherein the carbon-based material may include graphite (e.g., natural graphite, artificial graphite), non-graphitized carbon (soft carbon, hard carbon, etc.); the silicon-based material may include one or more of elemental silicon, silicon-based alloys, silicon oxides, silicon-carbon composites, and the like; the tin-based material may include one or more of elemental tin, tin alloys, and the like. The separator 103 may be a polymer separator, a nonwoven fabric, etc., including but not limited to a single layer PP (polypropylene), a single layer PE (polyethylene), a double layer PP/PE, a double layer PP/PP, and a triple layer PP/PE/PP, etc. Electrolyte 104 includes a lithium salt and a solvent, which may include one or more of carbonate solvents, carboxylate solvents, and ether solvents.
The electrochemical cell of the embodiment of the application can be used for end consumer products, such as products of mobile phones, tablet computers, mobile power supplies, portable computers, notebook computers, digital cameras and other wearable or movable electronic equipment, such as unmanned aerial vehicles, electric bicycles, electric vehicles and the like, so that the performance of the products is improved.
The embodiment of the application also provides electronic equipment comprising the electrochemical cell. The electronic device may be an electronic product including various consumer electronics such as a cell phone, tablet computer, notebook computer, mobile power supply, portable, and other wearable or removable electronic devices, televisions, video disc player, video recorder, camcorder, radio recorder, audio unit, record player, laser player, home office equipment, home electronics healthcare equipment, and automobile. It should be noted that, when the above electrochemical cell is applied to an electronic device, it may be accommodated in the electronic device in the form of a battery pack, and typically, the battery pack includes a plurality of battery modules (a single battery module may include a plurality of the above electrochemical cells), a battery management system for managing them, and the like.
In some implementations, referring to fig. 4, an embodiment of the present application provides an electronic device 200 that includes a housing 201 and electronic components (not shown in fig. 4) housed within the housing 201, and a battery 202, the battery 202 powering the electronic device 200, the battery 202 including the electrochemical cell 100 described above in the embodiments of the present application. The case 201 may include a front cover assembled at a front side of the terminal and a rear case assembled at a rear side, and the battery 202 may be fixed inside the rear case. The electronic device shown in fig. 4 is typically a small portable electronic device, such as a mobile phone.
In other embodiments, referring to fig. 5, an embodiment of the present application provides an electronic device 300, which may be various mobile devices for loading, transporting, assembling, disassembling, security, etc., and may be various forms of vehicles. Specifically, the electronic device 300 may include a vehicle body 301, a moving assembly 302, and a driving assembly including a motor 303 and a battery 304, where the battery 304 includes the electrochemical cell 100 provided in the embodiments of the present application. Wherein the moving assembly 302 may be a wheel. The battery 304 may be a battery pack containing the electrochemical cell 100 described above, which is housed in the underbody of the vehicle and is electrically connected to the motor 303 such that the electrochemical cell 100 may power the motor 303, and the motor 303 provides power to drive the moving assembly 302 of the electronic device 300.
The electrochemical cell that this application embodiment provided is through adopting its power supply to electronic equipment that this application embodiment provided, can satisfy all kinds of electronic equipment to battery high energy density, long cycle life's demand, promotes electronic equipment's use experience and market competition.
The embodiments of the present application are further described below in terms of a number of examples.
Example 1
A method of preparing a positive electrode lithium-replenishing agent comprising:
(1) Preparing a lithium supplementing agent precursor:
na is mixed with 2 Mixing S, se and Cr according to a molar ratio of 1:1:2:2, performing ball milling under an argon atmosphere, wherein the ball milling speed is 600r/min, the time is 30min, sintering the mixture obtained after ball milling under the argon atmosphere, wherein the sintering temperature is 800 ℃, the heat preservation time is 10h, and then cooling to room temperature to obtain a product NaCrSSe;
then NaCrSSe is combined with I 2 Adding the mixture into acetonitrile according to a certain molar ratio, fully mixing and reacting under argon atmosphere, and removing unreacted I 2 The reaction product was washed with acetonitrile, and adsorbed I was washed off 2 And (3) drying the simple substance in vacuum to obtain a precursor CrSSe.
The chemical reaction formula involved in the method is as follows: na (Na) 2 S+S+2Se+2Cr＝2NaCrSSe；2NaCrSSe+I 2 ＝2CrSSe+2NaI。
(2) Lithiation:
adding the CrSSe powder into ethylene glycol dimethyl ether solution of biphenyl lithium with the concentration of 0.1M, carrying out lithiation reaction for 20min to obtain a lithiated product, centrifuging to separate the lithiated product, and repeatedly cleaning with a solvent to obtain the positive electrode lithium supplementing agent, wherein the average chemical formula of the particle body of the positive electrode lithium supplementing agent is Li 3.5 CrSSe comprises the following substances in detail: li (Li) 3.5 CrSSe and LiCrSSe, li 2 S、Li 2 Se and Cr.
A method of making a lithium ion half-cell comprising:
1) Preparing a battery positive electrode plate:
adding the positive electrode lithium supplementing agent, a binder-polyvinylidene fluoride (PVDF) and a conductive agent-acetylene black into N-methylpyrrolidone (NMP) according to the weight ratio of 8:1:1, and uniformly stirring to obtain positive electrode slurry; coating the positive electrode slurry on a positive electrode current collector aluminum foil, and drying, rolling and cutting to obtain a positive electrode plate;
2) And (3) battery assembly: the positive pole piece is taken as a positive pole, a metal lithium piece is taken as a negative pole, a diaphragm is taken as celgard2400, and 1mol/L LiPF is adopted as electrolyte 6 Ethylene Carbonate (EC), ethylmethyl carbonate (EMC) and dimethyl carbonate (DMC); and (5) assembling in a glove box filled with argon to obtain the lithium ion half-cell.
The initial voltage for the first charge of the half cell of example 1 was an open circuit voltage (Open Circuit Voltage, OCV), approximately 1.3V, constant current charge (40 mA/g), and a charge cutoff voltage of 4.2V; the initial voltage of the first discharge was 4.2V, the constant current charge (40 mA/g), and the discharge cutoff voltage was 2.5V.
Example 2
A method of making a lithium ion half-cell comprising:
And (3) manufacturing a positive electrode plate: lithium iron phosphate (LiFePO) as positive electrode active material 4 ) Adding the positive electrode lithium supplementing agent prepared in the embodiment 1, a binder-polyvinylidene fluoride (PVDF) and a conductive agent-acetylene black into N-methylpyrrolidone (NMP) according to the weight ratio of 74:6:10:10, and uniformly stirring to obtain positive electrode slurry; coating the positive electrode slurry on a positive electrode current collector aluminum foil, and drying, rolling and cutting to obtain a positive electrode plate;
according to the method for manufacturing a half battery described in example 1, the positive electrode tab is assembled into a lithium ion half battery.
The half cell of example 2 was subjected to a charge-discharge cycle test in which the charge initiation voltage was OCV, about 2.3V,0.1c constant current charge, and the charge cut-off voltage was 4.2V; the initial voltage during discharging is 4.2V, the constant current charging is carried out at 0.1C, and the cut-off voltage is 2.7V.
To highlight the benefits of the present application, comparative examples 1 and 2 are set.
Comparative example 1
The positive electrode tab and half cell were fabricated according to the method described in example 1, using the lithium-compensating agent precursor CrSSe prepared in example 1 instead of the positive electrode lithium-compensating agent, and the half cell of comparative example 1 was charged and discharged for the first time according to the test conditions of example 1.
Comparative example 2
A lithium ion half-cell that differs from example 2 in that: the positive electrode lithium supplementing agent is not introduced, and the weight ratio of the positive electrode active material to the binder to the conductive agent is 80:10:10. The half cell of comparative example 2 was subjected to a charge-discharge cycle test according to the test conditions of example 2.
FIG. 6 is a particle bulk-Li of the positive electrode lithium-supplementing agent in example 1 of the present application 3.5 The results are characterized by an X-ray diffraction (XRD) of CrSSe and its precursor CrSSe. As can be seen from FIG. 6, the crystal structure of the precursor CrSSe is significantly changed after lithiation, the characteristic peak of CrSSe disappears, and Cr and Li can be observed in the lithium-supplementing agent obtained after lithiation 2 S、Li 2 Se, liCrSSe characteristic peaks, part of Li 3.5 CrSSe decomposition, the lithium supplement contains Cr, li 2 S、Li 2 Se and LiCrSSe.
Fig. 7 and 8 are the first charge and discharge curves of the half cell of example 1 and the half cell of comparative example 1, respectively. It can be seen that example 1 has an average chemical formula of Li 3.5 The lithium supplementing agent of CrSSe shows higher lithium removing capacity under the charge cut-off voltage of 4.2V>460 mAh/g), the lithium intercalation capacity is lower and is smaller than 40mAh/g, and the lithium intercalation capacity is negligible. From this, the lithium supplementing capacity (i.e., irreversible capacity) that the lithium supplementing agent can provide can be calculated>420mAh/g; while the CrSSe before lithiation used in comparative example 1 had negligible delithiation capacity<15 mAh/g), indicating Li after lithiation 3.5 CrSSe can be used as a lithium supplementing additive to have higher lithium supplementing capacity in the normal working potential range of the battery.
Fig. 9 is a comparative example 2 half cell (i.e., pure LiFePO 4 Button cell) and fig. 10 is a charge-discharge curve of a half cell of example 2 (LiFePO 4 Button cell mixed with positive electrode lithium-supplementing agent) and the broken line in fig. 9 and 10 represents the first charge-discharge cycle. As can be seen from fig. 9 to 10, liFePO in comparative example 2 4 The first charge specific capacity of the positive electrode is only 160mAh/g, and LiFePO with a certain lithium supplementing agent is added 4 The first-charge specific capacity of the positive electrode is as high as 199.6mAh/g, which indicates that the lithium supplementing agent of example 1 actually exerts a lithium supplementing capacity of 450mAh/g or more. In addition, in the subsequent charge-discharge cycle, the charge-discharge curve of the half cell of example 2 is basically consistent with that of the half cell of comparative example 2, and the specific capacity of the battery of example 2 is more stable, which indicates that the positive electrode lithium supplementing agent provided by the application plays a good role in supplementing lithium, and has no side effect on the cycle performance of the battery.
Example 3
A preparation method of a positive electrode lithium supplementing agent comprises the following steps:
(1) Preparing a lithium supplementing agent precursor:
li is mixed with 2 Mixing S, se and Cr according to a molar ratio of 1:1:2:2, performing ball milling under an argon atmosphere, wherein the ball milling speed is 800r/min, the time is 30min, vacuum sealing the mixture obtained after ball milling, and sintering under the argon atmosphere, wherein the sintering temperature is 900 ℃, the heat preservation time is 10h, and then cooling to room temperature to obtain a product LiCrSSe;
(2) Lithiation:
adding the LiCrSSe powder into ethylene glycol dimethyl ether solution of naphthalene lithium with the concentration of 0.1M, carrying out lithiation reaction for 10min to obtain a lithiated product, centrifuging to separate the product, and repeatedly cleaning with a solvent to obtain the positive electrode lithium supplementing agent, wherein the average chemical formula of the positive electrode lithium supplementing agent is Li 2.5 CrSSe。
Example 4
A preparation method of a positive electrode lithium supplementing agent comprises the following steps:
(1) Preparing a lithium supplementing agent precursor:
na is mixed with 2 Mixing S, se and Co according to a molar ratio of 1:1:2:2, performing ball milling under an argon atmosphere, wherein the ball milling speed is 600r/min, the time is 30min, sintering the mixture obtained after ball milling under the argon atmosphere, wherein the sintering temperature is 800 ℃, the heat preservation time is 10h, and then cooling to room temperature to obtain a product NaCoSSe;
NaCoSSe is then combined with I 2 Adding the mixture into acetonitrile according to a certain molar ratio, fully mixing and reacting under argon atmosphere, and removing unreacted I 2 The reaction product was washed with acetonitrile, and adsorbed I was washed off 2 And (3) the simple substance is dried in vacuum to obtain a precursor CoSSe.
(2) Lithiation:
adding the CoSSe powder into 0.1M ethylene glycol dimethyl ether solution of biphenyl lithium, performing lithiation reaction for 15min to obtain lithiated product, centrifuging to separate the product, and repeatedly cleaning with solvent to obtain positive electrode lithium supplementing agent with average chemical formula of Li 3 CoSSe。
Example 5
A preparation method of a positive electrode lithium supplementing agent comprises the following steps:
(1) Preparing a lithium supplementing agent precursor:
na is mixed with 2 Mixing S, se and Ti according to a molar ratio of 1:1:2:2, performing ball milling under an argon atmosphere, wherein the ball milling speed is 600r/min, the time is 30min, sintering the mixture obtained after ball milling under the argon atmosphere, wherein the sintering temperature is 900 ℃, the heat preservation time is 10h, and then cooling to room temperature to obtain a product which is NaTiSSe;
then NaTiSSe is combined with I 2 Adding the mixture into acetonitrile according to a certain molar ratio, fully mixing and reacting under argon atmosphere, and removing unreacted I 2 The reaction product was washed with acetonitrile, and adsorbed I was washed off 2 And (3) carrying out vacuum drying on the simple substance to obtain a precursor TiSSe.
(2) Lithiation:
adding the TiSSe powder into ethylene glycol dimethyl ether solution of 0.1M biphenyl lithium, performing lithiation reaction for 15min to obtain lithiated product, centrifuging to separate the product, and repeatedly cleaning with solvent to obtain positive electrode lithium supplementing agent with average chemical formula of Li 3 TiSSe。
Example 6
A preparation method of a positive electrode lithium supplementing agent comprises the following steps:
(1) Preparing a lithium supplementing agent precursor:
na is mixed with 2 Mixing S, se and V according to a molar ratio of 1:1:2:2, performing ball milling under an argon atmosphere, wherein the ball milling speed is 600r/min, the time is 30min, sintering the mixture obtained after ball milling under the argon atmosphere, wherein the sintering temperature is 950 ℃, the heat preservation time is 8h, and then cooling to room temperature to obtain a product which is NaVSSe;
Then NaVSSe is combined with I 2 Adding the mixture into acetonitrile according to a certain molar ratio, fully mixing and reacting under argon atmosphere, and removing unreacted I 2 The reaction product was washed with acetonitrile, and adsorbed I was washed off 2 And (3) obtaining a precursor VSSe after the simple substance is dried in vacuum.
(2) Lithiation:
adding the VSSe powder into ethylene glycol dimethyl ether solution of biphenyl lithium with the concentration of 0.1M, carrying out lithiation reaction for 20min to obtain a lithiated product, centrifuging to separate the product, and repeatedly cleaning with a solvent to obtain a positive electrode lithium supplementing agent, wherein the average chemical formula is Li 3.5 VSSe。
Example 7
A preparation method of a positive electrode lithium supplementing agent comprises the following steps:
(1) Preparing a lithium supplementing agent precursor:
na is mixed with 2 Mixing S, se and Mn according to a molar ratio of 1:1:2:2, performing ball milling under an argon atmosphere, wherein the ball milling speed is 600r/min, the time is 30min, sintering the mixture obtained after ball milling under the argon atmosphere, wherein the sintering temperature is 800 ℃, the heat preservation time is 10h, and then cooling to room temperature to obtain a product which is NaMnSSe;
then NaMnSSe is combined with I 2 Adding the mixture into acetonitrile according to a certain molar ratio, fully mixing and reacting under argon atmosphere, and removing unreacted I 2 The reaction product was washed with acetonitrile, and adsorbed I was washed off 2 And (3) carrying out vacuum drying on the simple substance to obtain a precursor MnSSe.
(2) Lithiation:
adding the MnSSe powder into 0.1M biphenyl lithium glycol dimethyl ether solution to carry out lithiation reactionObtaining lithiated product after 20min, centrifuging to obtain the product, and repeatedly cleaning with solvent to obtain positive electrode lithium supplementing agent with average chemical formula of Li 3.5 MnSSe。
Example 8
A preparation method of a positive electrode lithium supplementing agent comprises the following steps:
(1) Preparing a lithium supplementing agent precursor:
na is mixed with 2 Mixing S, se and Cr according to a molar ratio of 1:1:2:2, performing ball milling under an argon atmosphere, wherein the ball milling speed is 600r/min, the time is 30min, sintering the mixture obtained after ball milling under the argon atmosphere, wherein the sintering temperature is 800 ℃, the heat preservation time is 10h, and then cooling to room temperature to obtain a product NaCrSSe;
then NaCrSSe is combined with I 2 Adding the mixture into acetonitrile according to a certain molar ratio, fully mixing and reacting under argon atmosphere, and removing unreacted I 2 The reaction product was washed with acetonitrile, and adsorbed I was washed off 2 And (3) drying the simple substance in vacuum to obtain a precursor CrSSe.
(2) Lithiation:
Adding the CrSSe powder into ethylene glycol dimethyl ether solution of 0.1M biphenyl lithium, carrying out lithiation reaction for 15min to obtain lithiated product, centrifuging to separate the product, and repeatedly cleaning with solvent to obtain the positive electrode lithium supplementing agent with average chemical formula of Li 3 CrSSe。
Example 9
A preparation method of a positive electrode lithium supplementing agent comprises the following steps:
(1) Preparing a lithium supplementing agent precursor:
na is mixed with 2 Mixing S, se and Cr according to a molar ratio of 1:2:1:2, performing ball milling under an argon atmosphere, wherein the ball milling speed is 600r/min and the time is 30min, sintering the mixture obtained after ball milling under the argon atmosphere, wherein the sintering temperature is 800 ℃, the heat preservation time is 10h, and then cooling to room temperature to obtain the product NaCrS 1.5 Se 0.5 ；
Then NaCrS is added 1.5 Se 0.5 And I 2 Adding the mixture into acetonitrile according to a certain molar ratio, fully mixing and reacting under argon atmosphere, and removing unreacted I 2 The reaction product was washed with acetonitrile, and adsorbed I was washed off 2 Simple substance, and is dried in vacuum to obtain a precursor CrS 1.5 Se 0.5 。
(2) Lithiation:
the CrS is treated with 1.5 Se 0.5 Adding the powder into 0.1M ethylene glycol dimethyl ether solution of biphenyl lithium, performing lithiation reaction for 20min to obtain lithiated product, centrifuging to separate the product, and repeatedly cleaning with solvent to obtain the positive electrode lithium supplementing agent with average chemical formula of Li 3.5 CrS 1.5 Se 0.5 。
Example 10
A preparation method of a positive electrode lithium supplementing agent comprises the following steps:
(1) Preparing a lithium supplementing agent precursor:
na is mixed with 2 Mixing S, se and Cr according to a molar ratio of 1:3:2, performing ball milling under an argon atmosphere, wherein the ball milling speed is 600r/min and the time is 30min, sintering the mixture obtained after ball milling under the argon atmosphere, wherein the sintering temperature is 800 ℃, the heat preservation time is 10h, and then cooling to room temperature to obtain the NaCrS product 0.5 Se 1.5 ；
Then NaCrS is added 0.5 Se 1.5 And I 2 Adding the mixture into acetonitrile according to a certain molar ratio, fully mixing and reacting under argon atmosphere, and removing unreacted I 2 The reaction product was washed with acetonitrile, and adsorbed I was washed off 2 Simple substance, and is dried in vacuum to obtain a precursor CrS 0.5 Se 1.5 。
(2) Lithiation:
the CrS is treated with 0.5 Se 1.5 Adding the powder into 0.1M ethylene glycol dimethyl ether solution of biphenyl lithium, performing lithiation reaction for 20min to obtain lithiated product, centrifuging to separate the product, and repeatedly cleaning with solvent to obtain the positive electrode lithium supplementing agent with average chemical formula of Li 3.5 CrS 0.5 Se 1.5 。
The positive electrode lithium-compensating agents of examples 3 to 10 were prepared into positive electrode sheets, respectively, and assembled into button cells according to the method described in example 2, and each button cell was subjected to charge and discharge test with a voltage range of corresponding OTC to 4.2V, the charge and discharge curves thereof were recorded, and the comparative example 2 half cell containing only the positive electrode active material was combined, and the lithium removal specific capacity of each lithium-compensating agent was calculated, and the results are shown in table 1.
In addition, the positive electrode lithium supplementing agent of each embodiment is respectively assembled into full batteries, and after the assembled full batteries are formed, positive electrode active materials and negative electrode active materials in the battery core are activated, a stable SEI film is formed on the negative electrode, and the self-discharge performance, the charge-discharge performance, the storage performance and the like of the battery are improved. The assembly process of the full battery comprises the following steps: graphite pole piece is used as a negative electrode, diaphragm is used as celgard2400, and electrolyte adopts 1mol/L LiPF 6 Ethylene Carbonate (EC), ethylmethyl carbonate (EMC) and dimethyl carbonate (DMC); and (5) assembling in a glove box filled with argon to obtain the lithium ion full battery.
The specific process of the formation is as follows: after the full battery is assembled, the full battery is firstly kept stand for 4 hours at the temperature of 25 ℃, then is charged to 4.2V at a constant current with the multiplying power of 0.05C, and is charged to the charging current of <0.005C at a constant voltage of 4.2V. Then, each full cell after formation was subjected to charge-discharge cycle at 0.2C, voltage range: and 2.7V-4.2V, and testing the initial coulomb efficiency, specific discharge capacity, cycle performance and the like. The first charge here refers to the charge at the time of formation, and is not the first charge after the battery leaves the factory (actually, the second charge).
In addition, the application also provides LiFePO without adding the anode lithium supplement agent under the same condition 4 Results of performance test of full cell (comparative example 2).
Table 1 summary of test results for half cells of each example and comparative example
Table 2 summary of test results for full cells of each example and comparative example
The average chemical formula in the above embodiments of the present application is Li x MS y Se 2-y M can be suitable for various transition metals, y can take different values, and x can also take different values, and can be controlled by regulating and controlling the lithiation process. As can be known from the half-cell data in table 1, the lithium-supplementing agent in the embodiment of the present application is irreversibly decomposed in the first cycle, and the specific lithium removal capacity can exceed 450mAh/g, which indicates that the lithium-supplementing agent has a high lithium-supplementing capacity. After the half cell is cycled for 100 circles, the capacity retention rate is similar to that of comparative example 2 (half cell without lithium supplementing agent), which shows that the lithium supplementing agent has no obvious side effect on the positive electrode in the cycle and has good compatibility.
As can be known from the full-cell data in table 2, the lithium supplementing agent in the embodiment of the present application is irreversibly decomposed in the first cycle, and the first discharge specific capacity of the full cell is increased from 144mAh/g to more than 155mAh/g, even up to 160mAh/g, which indicates that the lithium supplementing agent can compensate the loss of active lithium of the negative electrode, and part of pre-stored lithium is stored in the negative electrode, thereby improving the cycle performance and energy density of the battery core. After the lithium supplementing agent is added into the full battery for 100 circles, the capacity retention rate of the full battery is obviously superior to that of the full battery without the lithium supplementing agent, which shows that the energy density of the battery after the lithium supplementing agent is added into the full battery is improved, the cycle performance is obviously improved, no other side effect is caused on the positive electrode, and the compatibility is good.
The first cycle coulombic efficiency of the full cell of comparative example 2 in table 2 is higher than that of examples 2 to 10, mainly because the first charge in table 2 is charge at the time of formation, the calculation of the cycle capacity retention rate is also based on the formation data as a comparison criterion, the first cycle coulombic efficiency of comparative example 2 without lithium supplementation is the first effect after the consumption of the negative electrode and the positive electrode, that is, the loss part thereof is irreversibly active lithium of the positive electrode, the discharge specific capacity at the 2 nd and subsequent cycles is low, and the cycle performance is poor. In the full battery of each example added with the lithium supplementing agent, the active lithium provided by the lithium supplementing agent is consumed in the first cycle (in formation) and the positive electrode active material is not consumed, but the coulombic efficiency of the 2 nd cycle and the following cycles is not low although the first cycle is low; and the discharge specific capacity is high, the cycle performance is good, and the energy density of the battery is correspondingly higher.
Claims (13)
1. The positive electrode lithium supplementing agent is characterized by comprising a particle body, wherein the particle body comprises a lithium compound of a sulfur selenide of a transition metal, and the average chemical formula of the lithium compound of the sulfur selenide of the transition metal is Li x MS y Se 2-y Wherein x is more than 1 and less than or equal to 4, y is more than 0 and less than 2, and M represents transition metal.
2. The positive electrode lithium-supplementing agent according to claim 1, wherein said particle body comprises a compound of the general formula Li x MS y Se 2-y Is a compound of (2) and M, li 2 S and Li 2 Se。
3. The positive electrode lithium-compensating agent of claim 2, wherein said particulate body further comprises a compound of the general formula LiMS y Se 2-y Is a compound of (a).
4. The positive electrode lithium supplement of any one of claims 1-3, wherein said M comprises one or more of Cr, ti, V, co, fe, ni, mn, nb.
5. The positive electrode lithium-supplementing agent according to any one of claims 1 to 4, wherein the surface of the particle body further has a coating layer.
6. The preparation method of the positive electrode lithium supplementing agent is characterized by comprising the following steps of:
mixing a transition metal source, a sulfur source and a selenium source, ball milling and sintering to prepare a sulfur selenide of the transition metal;
lithiation is carried out on the sulfur selenide of the transition metal to obtain a positive electrode lithium supplementing agent; wherein the positive electrode lithium supplementing agent comprises a particle body, the particle body comprises a lithium compound of a sulfur selenide of a transition metal, and the average chemical formula of the lithium compound of the sulfur selenide of the transition metal is Li x MS y Se 2-y Wherein x is more than 1 and less than or equal to 4, y is more than 0 and less than 2, and M represents transition metal.
7. A battery positive electrode sheet, wherein the battery positive electrode sheet contains the positive electrode lithium supplementing agent according to any one of claims 1 to 5.
8. The battery positive electrode tab of claim 7, wherein the battery positive electrode tab comprises a current collector and a positive electrode material layer disposed on the current collector, the positive electrode material layer comprising a positive electrode active material, the positive electrode lithium-compensating agent, and a binder.
9. The battery positive electrode sheet according to claim 7, wherein the battery positive electrode sheet comprises a current collector, and a positive electrode material layer and a lithium supplementing agent layer which are sequentially arranged on the current collector, wherein the positive electrode material layer contains a positive electrode active material, a binder and a conductive agent, and the lithium supplementing agent layer contains the positive electrode lithium supplementing agent, the binder and the conductive agent.
10. The battery positive electrode sheet according to claim 8 or 9, wherein the ratio of the mass of the positive electrode lithium-supplementing agent to the sum of the mass of the positive electrode lithium-supplementing agent and the mass of the positive electrode active material is 1% to 10%.
11. The battery positive electrode sheet according to claim 8, wherein the mass of the positive electrode lithium supplementing agent is 0.5% -15% of the mass of the positive electrode material layer.
12. An electrochemical cell comprising a positive electrode, a negative electrode, and a separator and electrolyte between the positive electrode and the negative electrode, wherein the positive electrode is the positive electrode sheet of the cell of any one of claims 7-11.
13. An electronic device having the electrochemical cell of claim 12.
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| CN202210031227.7A CN116470048A (en) | 2022-01-12 | 2022-01-12 | Positive electrode lithium supplementing agent, preparation method and application thereof |
| PCT/CN2023/071097 WO2023134589A1 (en) | 2022-01-12 | 2023-01-06 | Positive electrode lithium supplementing agent, and preparation method therefor and use thereof |
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| CN202210031227.7A CN116470048A (en) | 2022-01-12 | 2022-01-12 | Positive electrode lithium supplementing agent, preparation method and application thereof |
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| CN109728253A (en) * | 2018-12-27 | 2019-05-07 | 江西星盈科技有限公司 | Lithium ion battery and its positive plate and preparation method thereof |
| CN111384428B (en) * | 2018-12-29 | 2021-09-17 | 宁德时代新能源科技股份有限公司 | Lithium supplement agent, positive pole piece, isolating membrane and lithium ion battery |
| CN110993933A (en) * | 2019-10-21 | 2020-04-10 | 肇庆遨优动力电池有限公司 | Positive electrode material of lithium ion battery, preparation method and lithium ion battery |
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