CN117335022A - High-stability positive electrode lithium supplementing material, preparation method thereof and lithium ion battery - Google Patents
High-stability positive electrode lithium supplementing material, preparation method thereof and lithium ion battery Download PDFInfo
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- CN117335022A CN117335022A CN202311349303.XA CN202311349303A CN117335022A CN 117335022 A CN117335022 A CN 117335022A CN 202311349303 A CN202311349303 A CN 202311349303A CN 117335022 A CN117335022 A CN 117335022A
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 141
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 137
- 239000000463 material Substances 0.000 title claims abstract description 116
- 230000001502 supplementing effect Effects 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 90
- 239000011159 matrix material Substances 0.000 claims abstract description 84
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 71
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 69
- 238000000034 method Methods 0.000 claims abstract description 46
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- 238000000151 deposition Methods 0.000 claims abstract description 14
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- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
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- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 6
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- JXGGISJJMPYXGJ-UHFFFAOYSA-N lithium;oxido(oxo)iron Chemical compound [Li+].[O-][Fe]=O JXGGISJJMPYXGJ-UHFFFAOYSA-N 0.000 description 6
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- 239000007774 positive electrode material Substances 0.000 description 4
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
-
- 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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
-
- 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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- 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
-
- 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
- H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
-
- 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
- H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
- H01M4/602—Polymers
- H01M4/604—Polymers containing aliphatic main chain polymers
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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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a high-stability positive electrode lithium supplementing material, a preparation method thereof and a lithium ion battery. The method comprises the steps of depositing coated metal oxide on the surface of a lithium-rich iron core matrix by ALD, capturing residual lithium in a deposition heating process to form a fast ion conductor layer, and obtaining a pre-coated matrix; modifying the carbon source by a coupling agent to obtain a pretreated carbon source; and premixing the pretreated carbon source and the organic nano powder, and then carrying out dry or wet mixed coating with the precoated matrix, and carrying out heat treatment to obtain the high-stability positive electrode lithium supplementing material. The prepared positive electrode lithium supplementing material comprises a core lithium-rich iron matrix, a fast ion conductor layer and an organic-inorganic conductive carbon layer which can be communicated with an organic-inorganic interface and has a rigid structure and hydrophobicity from inside to outside; the method can solve the problems of poor stability, large alkalinity, large impedance, poor coating effect, impure phase caused by carbothermic reduction, poor compatibility with solvents and electrolyte, capacity loss caused by inert hydrophobic layers, poor conductivity and the like of the conventional positive electrode lithium supplementing material.
Description
Technical Field
The invention relates to a positive electrode lithium supplementing material, in particular to a high-stability positive electrode lithium supplementing material, a preparation method thereof and a lithium ion battery, and belongs to the technical field of positive electrode materials of lithium ion batteries.
Technical Field
In the first charging process of the lithium ion battery, the organic electrolyte is reduced and decomposed on the surface of a negative electrode such as graphite to form a solid electrolyte phase interface (SEI) film, so that a large amount of lithium from a positive electrode is permanently consumed, and the coulombic efficiency (ICE) of the first cycle is low, thereby reducing the capacity and the energy density of the lithium ion battery.
To solve this problem, lithium is often supplied to the positive electrode to offset the irreversible lithium loss caused by the formation of the SEI film, thereby improving the total capacity and energy density of the battery. Typical positive electrode lithium supplementation is to add a small amount of high-capacity material in the positive electrode slurry mixing process, and Li in the charging process + Is separated from the lithium-rich material to supplement irreversible capacity loss of primary charge and discharge. The positive electrode lithium supplementing has the most industrial application prospect because of high safety and no need of changing the existing battery production process. At present, materials used as positive electrode lithium supplementing additives mainly comprise: lithium-richCompounds, nanocomposite materials based on conversion reactions, binary lithium compounds, and the like.
However, in research and practical application, the existing positive electrode lithium supplementing additive has the following problems: (1) The chemical stability in the air is poor, the structure is unstable, and the deterioration is easy, so that the purity is reduced due to the processing process; (2) The bulk lithium is easy to separate out when contacting with air or a humid environment, so that residual alkali is raised, and gel phenomenon is easy to occur when the battery is homogenized; (3) The impedance is larger, the conductivity is poor, and the addition can influence the cycle performance and the multiplying power performance of the battery; (4) In the charge and discharge process, the electrolyte is easy to undergo side reaction due to the factors of material phase change, heat generation, surface residual alkali and the like, and a large amount of gas is generated; (5) The material particles have strong corrosiveness and strong water absorbability, have strong agglomeration effect and are extremely easy to oxidize, so that the moisture content must be strictly controlled in the use process, and a large amount of residual alkali can be generated once water is absorbed, so that equipment is lost.
Based on the problems in the above preparation and use, the existing solutions are mainly by: the solution is achieved by means of generating a synergistic effect by using the composite lithium salt, adding additives into the electrolyte, adding a water washing process, coating and the like, wherein the most effective means is surface coating modification. Such as:
chinese patent document CN113178567a discloses a positive electrode lithium supplementing material and a lithium ion battery including the same. The zirconium dioxide is particularly adopted to carry out surface coating on lithium nickel acid lithium rich, on one hand, the zirconium dioxide is used as an inactive material, has a porous structure, inhibits the corrosion of Hydrogen Fluoride (HF) in electrolyte to protect the lithium nickel acid lithium rich, and can simultaneously allow free deintercalation of lithium ions; on the other hand, the residual lithium on the surface of the lithium nickel acid can react with the residual lithium on the surface of the lithium nickel acid, so that the residual alkali number of the material is reduced, and the gas production problem of the battery is effectively inhibited. However, this solution simply uses Li 2 NiO 2 Co-nanoscale ZrO 2 The high-speed mixer is used for mixing, coating and sintering, the coating is not uniform, more exposed surfaces which are contacted with air still exist, and the effect of improving the conductivity is not great.
Chinese patent document CN110459748A discloses a carbon-coated lithium ferrite material and a preparation method thereof. By usingThe carbon source is subjected to gas phase coating to isolate the external environment, so that the contact between lithium ferrite and water in the air is relieved, and the stability of the material is improved; the gas phase cladding process comprises the following steps: placing the crushed lithium ferrite into a CVD rotary furnace, heating to a preset temperature, introducing a carbon source (one or more of methane, ethane, propane, ethylene, acetylene and butylene), coating in a gas phase at the preset temperature, stopping introducing the carbon source, and cooling to obtain a carbon-coated lithium ferrite material; the preset coating temperature is 600-800 ℃. However, in this embodiment, the carbon source generates a reducing gas during the cracking process, and it is known from the Enhame chart that Fe is contained in the presence of the reducing gas 3+ At a temperature higher than 710 ℃, the Fe is changed into the Fe which exists stably, at a temperature between 680 and 710 ℃, the Fe is changed into the FeO which exists stably, and at a temperature lower than 680 ℃, the Fe is mainly used 3 O 4 Exists. The method of directly coating the lithium ferrite and the carbon source can easily obtain various crystal forms of mixed materials, which results in low purity of the lithium ferrite, such as Li generation 5 Fe 5 O 8 、LiFeO 2 、Li 5 FeO 4 And Fe mixed phase. In addition, the coated carbon is often amorphous carbon, the specific surface area is large and loose, the compatibility with solvents and electrolyte is poor, the coated carbon can be rapidly peeled off from the core material when placed in the solvents and floats on the surface of the solution, and the protection effect on the core material is small.
Chinese patent document CN116137323a discloses a positive electrode lithium supplementing additive, and a preparation method and application thereof. The positive electrode lithium supplementing additive comprises a lithium-containing inner core and a coating layer formed on the surface of the lithium-containing inner core, wherein the material of the coating layer is selected from conductive hydrophobic polymers with surface modified hydrophobic reinforcing agents, the hydrophobic reinforcing agents are selected from fluorine-containing silane coupling agents, and the conductive hydrophobic polymers comprise one or more of polyacetylene, polyaniline, polypyrrole, polythiophene, polyphenylene, polyparaphenylene ethylene and derivatives thereof; the coating layer is formed, so that on one hand, the defect of poor electronic conductivity of the lithium-containing compound can be overcome, the electronic conductivity is improved, meanwhile, the lithium-containing compound can serve as a conductive agent in the electrode plate, and the addition amount of the conductive agent in the electrode plate is reduced; on the other hand, as the surface of the polymer is modified with the hydrophobic reinforcing agent to provide hydrophobic groups, the hydrophobic barrier is further arranged, so that the stability of the lithium-containing inner core in the air is effectively improved, the contact reaction of water and carbon dioxide in the air with the inner core lithium-supplementing material is effectively blocked, the lithium-containing compound is prevented from reacting with water to fail, and the stability of the lithium-supplementing material is protected. However, in all reports, the actual electron conductivity of the conductive polymer is not high, and the capacity of the active material is greatly compromised.
Therefore, it is needed to provide a positive electrode lithium supplementing material capable of solving the above problems.
Disclosure of Invention
The invention aims to provide a high-stability positive electrode lithium supplementing material, a preparation method thereof and a lithium ion battery. The method aims to solve the problems of poor stability, large alkalinity, large impedance, poor coating effect, impure phase caused by carbothermic reduction, poor compatibility with solvents and electrolyte, poor capacity loss and poor conductivity of a battery caused by an inert hydrophobic layer and the like of a positive electrode lithium supplementing material in the prior art.
In order to solve the technical problems, the invention adopts the following technical scheme:
in a first aspect, the invention provides a preparation method of a high-stability positive electrode lithium supplementing material, which specifically comprises the following steps:
(1) Preparing a lithium-rich iron core matrix material;
(2) Depositing coated metal oxide on the surface of the lithium-rich iron core matrix material by ALD, capturing residual lithium in the ALD deposition heating process to form a fast ion conductor layer, and obtaining a pre-coated matrix;
(3) Pretreatment of carbon source: modifying a carbon source by a coupling agent to obtain a pretreated carbon source, wherein the carbon source is a low-temperature easy-carbonization carbon source with carbonization temperature lower than 260 ℃;
(4) Premixing the pretreated carbon source prepared in the step (3) with organic nano powder in a preset proportion, then carrying out dry or wet mixed coating on the pretreated carbon source and the precoated matrix obtained in the step (2), carrying out heat treatment in an inert atmosphere, and carrying out crushing, dissociation and classification on the heat-treated material to obtain the high-stability positive electrode lithium supplementing material.
ALD deposition, referred to herein as atomic layer deposition (Atomic layer deposition), is a process whereby materials can be plated onto a substrate surface layer by layer in a monoatomic film. The specific ALD deposition process of the present invention is not limited, and the key point is to deposit a metal oxide coating the core matrix material by ALD at a predetermined mass ratio.
Further, the method comprises the steps of,
in the step (1), the molecular formula of the lithium-rich iron-based core matrix material is Li x Fe y M z O 4 The method comprises the steps of carrying out a first treatment on the surface of the Wherein Fe ions are trivalent, x is more than or equal to 4.0 and less than or equal to 6.0,0.85, y is more than or equal to 1.0, z is more than or equal to 0 and less than or equal to 0.15, and z=1-y;
when 0<z is less than or equal to 0.15, M is one or more metal elements selected from Co, ni, mn, nb, al, ti, zr, si, cr, V, mo, and the valence state of M metal ions is greater than or equal to positive trivalent.
In the present invention, fe is not changed for doping the element M 3+ Ion valence state is mainly that ferric iron valence state cannot be reduced, so that crystalline phase impurity requires that M ion valence state is larger than or equal to positive trivalent.
When z=0, the molecular formula of the lithium-rich iron-based core matrix material does not contain the doping element M.
Further, the method comprises the steps of,
in the step (2), the metal element in the ALD deposited metal oxide is at least one of Zn, cr, mn, si, ti, al, mg, ca, W; the ion valence states of the metal elements are the lowest stable valence states except zero valence; the metal element in the metal oxide accounts for 0.02-2% of the mass of the lithium-rich iron core matrix material.
Further, the method comprises the steps of,
in the step (3), the carbon source is one or more of carbohydrate, low molecular organic matter or petroleum lysate with carbonization temperature lower than 260 ℃. Preferably, the carbon source is one or two or more of starch, lignite and bituminous coal.
Further, the method comprises the steps of,
in the step (3), the coupling agent is a silane coupling agent. Preferably, the coupling agent is a KH560 silane coupling agent. KH560 is named gamma-glycidol ether oxypropyl trimethoxy silane with CAS number 2530-83-8, and is a coupling agent containing epoxy group.
Further, the method comprises the steps of,
the step of pretreating the carbon source in the step (3) is specifically to dip the carbon source into the coupling agent liquid for uniform mixing or spray the coupling agent liquid into the carbon source for uniform mixing, and then dry for 2-24 hours at the temperature lower than 60 ℃ in the air or vacuum environment.
Further, the method comprises the steps of,
the carbon source accounts for 0.5-10% of the mass of the lithium-rich iron core matrix material; the mass ratio of Si element in the coupling agent to the lithium-rich iron core matrix material is 0.01-0.1%.
Further, the method comprises the steps of,
the organic nanopowder in step (4) comprises PTFE which acts as a rigid structure, and one or two or more of PVDF, PAN, PMMA which acts as a hydrophobic and is soluble in NMP.
The organic nano-powder which plays a role in hydrophobicity and is soluble in NMP can be melted to form linear bonding and a coating layer during the heat treatment process so that the material becomes inert.
Further, the method comprises the steps of,
the PTFE with the function of rigid structure accounts for 0.01 to 1 percent of the mass of the carbon source; the organic nano powder which plays a role in hydrophobicity and can be dissolved in NMP accounts for 0.01-50% of the carbon source by mass.
Further, the method comprises the steps of,
in the step (4), the inert atmosphere in the heat treatment process is at least one of nitrogen and argon, and the inert atmosphere needs to be controlled to have the oxygen concentration below 50 ppm; the heat treatment temperature is 60-260 ℃; the heat treatment time is 2-24 hours.
Further, the method comprises the steps of,
the lithium-iron-rich core particle matrix material of the step (1) is prepared by the following method: uniformly mixing a lithium source, an iron source and an M source, and carrying out high-temperature sintering heat treatment in an inert atmosphere, wherein the heat treatment temperature is 400-900 ℃; the heat treatment time is 2-24 hours; crushing and grading in an inert atmosphere to obtain the lithium-rich iron core particle matrix material powder.
Further, the lithium source includes: li (Li) 2 O，LiOH，Li 2 C 2 O 4 ，Li 2 CO 3 One or two or more of the following.
Further, the iron source includes: fe (Fe) 2 O 3 ，Fe 2 (C 2 O 4 ) 3 ，Fe(NO 3 ) 3 One or two or more of the following.
Further, the element M in the M source is at least one metal element selected from Co, ni, mn, nb, al, ti, zr, si, cr, V, mo, and the valence state of M metal ions is more than or equal to positive trivalent.
When z=0, the lithium-rich iron-based core particle matrix material is not doped with M element.
Further, the lithium source is added to the iron source and the M source in a ratio of (4-6): 1, wherein the ratio of the number of moles of lithium element to the sum of the moles of iron element and M element is equal to (4-6).
Further, the M source comprises one or two or more of oxide, hydroxide and carbonate containing M element.
Further, the M source and the iron source are added according to the molar ratio of M element to iron element of (0-0.15): (0.85-1).
Further, the inert atmosphere is at least one of nitrogen and argon, and the oxygen concentration of the inert atmosphere needs to be controlled below 50 ppm. The lithium-rich iron core particle matrix material is in a single-particle crystal or spheroid morphology, and the medium particle size is 1-20 microns.
In a second aspect, the invention also provides the high-stability positive electrode lithium supplementing material prepared by the method, which comprises a lithium-rich iron core matrix material, a fast ion conductor layer which is uniformly and densely coated on the surface of the lithium-rich iron core matrix material, and an organic-inorganic conductive carbon layer which is capable of being communicated with an organic-inorganic interface and has a rigid structure and hydrophobicity and is coated on the surface of the fast ion conductor layer. The high-stability positive electrode lithium supplementing material is in a single-particle crystal or spheroid shape, and the medium particle size is 1-20 microns.
The invention also provides a lithium ion battery, which comprises a positive electrode plate, wherein the positive electrode slurry for preparing the positive electrode plate comprises the high-stability positive electrode lithium supplementing material prepared by the method. The high-stability positive electrode lithium supplementing material prepared by the method is generally mixed with a positive electrode active material for pulping.
The invention also provides electric equipment, which comprises the lithium ion battery.
Compared with the prior art, the invention has the beneficial effects that:
1. the preparation method provided by the invention is to deposit a layer of compact metal oxide which is not easy to be reduced by carbothermic reaction on the surface of the lithium-rich iron core matrix material by ALD, consume residual lithium in the ALD heating process and lock active lithium. The reason that the metal oxide is not easy to be reduced by carbothermic reaction is that the ion valence state of the metal element in the metal oxide coated by deposition is the lowest stable valence state except zero valence, and the residual lithium on the surface of the core matrix material can also react with the residual lithium to obtain a fast ion conductor in the ALD heating process to form a fast ion conductor layer, and the fast ion conductor coating layer can not only isolate the reducing gas generated by the subsequent carbon source cracking from Fe in the internal matrix 3+ While also increasing electron and ion conductivity.
2. According to the preparation method provided by the invention, after the carbon source is modified by the silane coupling agent, a chemical bond can be established between the organic matter and the inorganic matter, so that one end of the carbon source is provided with an organic group with the organic matter, the other end of the carbon source is provided with a silicon-oxygen bond with the inorganic matter, and the two ends of the carbon source are connected through the carbon-silicon bond, and an organic-inorganic interface is established, thereby realizing that the material is quickly soaked by electrolyte in the battery, and reducing the activation time.
3. According to the preparation method, the pretreated carbon source with low carbonization temperature is mixed with the organic nano powder, then the pre-coated substrate coated by the fast ion conductor layer is further coated, and the carbonization of the carbon source and the non-decomposition of the silane coupling agent are ensured, the melting of the hydrophobic organic nano powder is ensured, the non-decomposition and the non-carbonization of PTFE with a rigid structure are ensured, and the non-melting, the non-decomposition and the non-carbonization of PTFE with a rigid structure are ensured through the temperature control of low temperature heat treatment.
4. The high-stability positive electrode lithium supplementing material prepared by the preparation method provided by the invention needs to be mixed with a positive electrode active material for pulping, and has the following performance advantages:
(1) The material is in an inert state before being not used, can exist stably for a long time, and the surface hydrophobic energy isolates water and oxygen to improve the processing performance.
(2) The high-stability positive electrode lithium supplementing material is characterized in that the linear bonding and coating layer can be dissolved in NMP in the battery pulping process, an inert state is broken, and the release material is activated.
(3) The high-stability positive electrode lithium supplementing material establishes an organic-inorganic two-phase interface, and realizes rapid infiltration and activation of electrolyte.
(4) The insoluble PTFE in the high-stability positive electrode lithium supplementing material can strengthen the coating layer, so that floating carbon cannot be generated in the pulping process, and meanwhile, a multipurpose channel is formed along with the dissolution of part of the coating layer, so that the infiltration of the material and the movement of ions and electrons are facilitated.
(5) The carbon coating layer in the high-stability positive electrode lithium supplementing material can improve electronic conductivity and reduce impedance, and after the lithium supplementing material releases Li in the first charging process, residual non-electrochemical active substances can not increase the impedance of the positive electrode plate due to the fact that the residual non-electrochemical active substances coat the electronic and ionic conductors.
And the internal lithium-obtaining fast ion conductor oxide coating layer can also improve the ion conductivity and reduce the interface impedance.
The high-stability positive electrode lithium supplementing material provided by the invention can be used for pulping by being mixed with the positive electrode active material, so that the capacity and the energy density of a lithium ion battery can be improved.
Drawings
In order to more clearly illustrate the embodiments of the invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, it being obvious that the drawings in the following description are only some embodiments of the invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 shows a positive electrode lithium-supplementing material and Li obtained in example 1 of the present invention 5 FeO 4 XRD pattern of standard card;
FIG. 2 shows the embodiment of the present inventionThe positive electrode lithium-supplementing material obtained in example 2 was mixed with Li 5 FeO 4 XRD pattern of standard card;
FIG. 3 shows a positive electrode lithium-supplementing material and Li obtained in example 3 of the present invention 5 FeO 4 XRD pattern of standard card;
FIG. 4 shows a positive electrode lithium-supplementing material and Li obtained in example 4 of the present invention 5 FeO 4 XRD pattern of standard card;
FIG. 5 shows the positive electrode lithium-supplementing material and Li obtained in example 5 of the present invention 5 FeO 4 XRD pattern of standard card;
fig. 6 is an SEM image of the positive electrode lithium-compensating material obtained in example 1 of the present invention at 5000 times magnification;
fig. 7 is an SEM image of the positive electrode lithium-compensating material obtained in example 1 of the present invention at 10000 times magnification;
fig. 8 is a TEM image of a single particle of the positive electrode lithium-compensating material obtained in example 1 of the present invention;
fig. 9 is a TEM image of a single particle of the positive electrode lithium-compensating material obtained in example 2 of the present invention;
FIG. 10 is a TEM image of single particles of the positive electrode lithium-compensating material obtained in example 3 of the present invention;
FIG. 11 is a TEM image of single particles of the positive electrode lithium-compensating material obtained in example 4 of the present invention;
FIG. 12 is a TEM image of single particles of the positive electrode lithium-compensating material obtained in example 5 of the present invention;
fig. 13 is a graph showing the first charge and discharge of the positive electrode lithium-compensating material obtained in example 1 of the present invention and 2032 button cell battery made of the conventional uncoated lithium-rich ferrite material of comparative example 1, respectively, at a normal temperature current density of 0.05C and a voltage of 2.8V to 4.5V.
Detailed Description
The term as used herein:
"prepared from … …" is synonymous with "comprising". The terms "comprising," "including," "having," "containing," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, step, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, step, method, article, or apparatus.
The conjunction "consisting of … …" excludes any unspecified element, step or component. If used in a claim, such phrase will cause the claim to be closed, such that it does not include materials other than those described, except for conventional impurities associated therewith. When the phrase "consisting of … …" appears in a clause of the claim body, rather than immediately following the subject, it is limited to only the elements described in that clause; other elements are not excluded from the stated claims as a whole.
When an equivalent, concentration, or other value or parameter is expressed as a range, preferred range, or a range bounded by a list of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when ranges of "1 to 5" are disclosed, the described ranges should be construed to include ranges of "1 to 4", "1 to 3", "1 to 2 and 4 to 5", "1 to 3 and 5", and the like. When a numerical range is described herein, unless otherwise indicated, the range is intended to include its endpoints and all integers and fractions within the range.
In these examples, the parts and percentages are by mass unless otherwise indicated.
"parts by mass" means a basic unit of measurement showing the mass ratio of a plurality of components, and 1 part may be any unit mass, for example, 1g may be expressed, or 2.77g may be expressed. If we say that the mass part of the a component is a part and the mass part of the B component is B part, the ratio a of the mass of the a component to the mass of the B component is represented as: b. alternatively, the mass of the A component is aK, and the mass of the B component is bK (K is an arbitrary number and represents a multiple factor). It is not misunderstood that the sum of the parts by mass of all the components is not limited to 100 parts, unlike the parts by mass.
"and/or" is used to indicate that one or both of the illustrated cases may occur, e.g., a and/or B include (a and B) and (a or B).
In order that the invention may be readily understood, a more complete description of the invention will be rendered by reference to the appended drawings. Preferred embodiments of the present invention are shown in the drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
Example 1
The embodiment provides a preparation method of a positive electrode lithium supplementing material, which comprises the following specific steps:
s1, preparing a lithium-rich iron core particle matrix material
Weighing Fe with corresponding weight according to the molar ratio of Li to Fe to Ti=5.1 to 0.99 to 0.01 2 O 3 、Li 2 O、TiO 2 Mixing uniformly in a high-speed mixer, placing the mixed material into a sagger, placing into a nitrogen furnace, heating to 850 ℃ at a speed of 5 ℃/min in a nitrogen atmosphere with an oxygen concentration of less than 50ppm, preserving heat for 15 hours, cooling, and mechanically crushing and grading the product in the nitrogen atmosphere to obtain the lithium-rich iron-based core particle matrix material Li 5.1 Fe 0.99 Ti 0.01 O 4 。
S2, preparing a pre-coated substrate
Placing the lithium-rich iron core particle matrix material obtained in the step S1 into a reaction chamber of an ALD device, vacuumizing, replacing nitrogen, heating the reaction chamber to 80 ℃, maintaining the reaction chamber at a certain pressure, rotating the reactor, and then carrying out atomic layer depositionPrecursor AlCl 3 Pulse into reaction chamber with nitrogen gas at proper flow rate, alCl 3 The Al content is 1.0% of the matrix material, the matrix material is adsorbed, the pulse time is adjusted according to the input amount of the matrix material until the air pressure reaches a certain value, then the residual precursor is purged with nitrogen with higher flow rate, the nitrogen purging time is dependent on the volume of the reactor, and then a certain amount of oxygen source steam H is introduced 2 O 2 Pulse into the reaction chamber under the carrying of nitrogen with a certain flow rate, and chemically adsorb AlCl on the matrix material 3 React to generate Al 2 O 3 The time is adjusted according to the input amount of the matrix material, and then excessive H is added 2 O 2 And the byproducts are flushed out of the reaction chamber by nitrogen with higher flow rate, the flushing time is adjusted according to the volume of the reactor, then the temperature of the reaction chamber is raised to 500 ℃ for heating for 4 hours under the nitrogen atmosphere, and the deposited Al is caused by capturing residual lithium in the ALD deposition heating process 2 O 3 And forming a fast ion conductor layer by the layer and the trapped residual lithium to obtain a pre-coated matrix.
S3, pretreatment of carbon source
Immersing starch accounting for 1.25% of the mass ratio of the matrix in KH560 liquid accounting for 0.08% of the mass ratio of the matrix and converted by Si element, uniformly mixing, and then vacuum drying at 50 ℃ for 12 hours to obtain the pretreated carbon source.
S4, premixing PTFE accounting for 0.05% of the mass ratio of the starch in the step S3, PVDF accounting for 5% of the mass ratio of the starch in the step S3 and a pretreated carbon source obtained in the step S3, uniformly mixing the pre-coated substrate obtained in the step S2 and the premix in a high-speed mixer, putting the mixture into a sagger, putting the sagger into a nitrogen furnace, heating to 200 ℃ at the speed of 3 ℃/min in the nitrogen atmosphere with the oxygen concentration of less than 50ppm, preserving heat for 6 hours, cooling, and mechanically crushing, classifying, sieving and removing magnetism to obtain the high-stability positive electrode lithium supplementing material in the air environment with the dew point of less than-20.
Example 2
The embodiment provides a preparation method of a positive electrode lithium supplementing material, which comprises the following specific steps:
s1, preparing a lithium-rich iron core particle matrix material
Weighing Fe with corresponding weight according to the molar ratio of Li to Fe to Al=5.3 to 0.95 to 0.05 2 O 3 、Li 2 O、Al 2 O 3 Mixing uniformly in a high-speed mixer, placing the mixed material into a sagger, placing into a nitrogen furnace, heating to 900 ℃ at a speed of 5 ℃/min in a nitrogen atmosphere with an oxygen concentration of less than 50ppm, preserving heat for 10 hours, cooling, and mechanically crushing and grading the product in the nitrogen atmosphere to obtain the lithium-rich iron-based core particle matrix material Li 5.3 Fe 0.95 Al 0.05 O 4 。
S2, preparing a pre-coated substrate
Placing the lithium-rich iron core particle matrix material obtained in the step S1 into a reaction chamber of an ALD device, vacuumizing, replacing nitrogen, heating the reaction chamber to 60 ℃, maintaining the reaction chamber at a certain pressure, rotating the reactor, and then, depositing a precursor ZnCl for atomic layer deposition 2 Pulsed into the reaction chamber with nitrogen at a suitable flow rate, znCl 2 The Zn content in the catalyst is 0.1% of the mass ratio of the matrix, the catalyst is adsorbed on the matrix material, the pulse time is adjusted according to the input amount of the matrix material until the air pressure reaches a certain value, then the catalyst is purged with nitrogen with higher flow rate and the residual precursor is taken away, the nitrogen purging time is dependent on the volume of the reactor, and then a certain amount of oxygen source steam H is introduced 2 O 2 Pulse into the reaction chamber under the carrying of nitrogen with a certain flow rate, and chemically adsorb ZnCl on the matrix material 2 The reaction is carried out to generate ZnO, the time is adjusted according to the input amount of the matrix material, and then excessive H is generated 2 O 2 The byproducts are taken out of the reaction chamber through nitrogen purging with higher flow rate, the purging time is adjusted according to the volume of the reactor, and then the temperature of the reaction chamber is increased to 400 ℃ for heating for 2 hours under the nitrogen atmosphere; and capturing residual lithium in the ALD deposition heating process, so that the deposited ZnO layer and the captured residual lithium form a fast ion conductor layer, and the pre-coated substrate is obtained.
S3, pretreatment of carbon source
Immersing starch accounting for 1.5% of the mass of the matrix in KH560 liquid accounting for 0.05% of the mass of the matrix and converted by Si element, uniformly mixing, and vacuum drying at 50 ℃ for 12 hours to obtain the pretreated carbon source.
S4, premixing PTFE accounting for 0.08% of the mass ratio of the starch in the step S3, PVDF accounting for 8% of the mass ratio of the starch in the step S3 and a pretreated carbon source obtained in the step S3, uniformly mixing the pre-coated substrate obtained in the step S2 and the premix in a high-speed mixer, putting the mixture into a sagger, putting the sagger into a nitrogen furnace, heating to 240 ℃ at the speed of 3 ℃/min in the nitrogen atmosphere with the oxygen concentration of less than 50ppm, preserving heat for 6 hours, cooling, and mechanically crushing, classifying, sieving and removing magnetism to obtain the high-stability positive electrode lithium supplementing material in the air environment with the dew point of less than-20.
Example 3
The embodiment provides a preparation method of a positive electrode lithium supplementing material, which comprises the following specific steps:
s1, preparing a lithium-rich iron core particle matrix material
Weighing Fe with corresponding weight according to the molar ratio of Li to Fe to Nb=5.2 to 0.88 to 0.12 2 O 3 、Li 2 O、Nb 2 O 5 Mixing uniformly in a high-speed mixer, placing the mixed material into a sagger, placing into a nitrogen furnace, heating to 800 ℃ at a speed of 5 ℃/min in a nitrogen atmosphere with an oxygen concentration of less than 50ppm, preserving heat for 15 hours, cooling, and mechanically crushing and grading the product in the nitrogen atmosphere to obtain the lithium-rich iron-based core particle matrix material Li 5.2 Fe 0.88 Nb 0.12 O 4 。
S2, preparing a pre-coated substrate
Placing the lithium-rich iron core particle matrix material obtained in the step S1 into a reaction chamber of an ALD device, vacuumizing, replacing nitrogen, heating the reaction chamber to 50 ℃, maintaining the reaction chamber at a certain pressure, rotating the reactor, and then carrying out atomic layer deposition on a precursor MnSO 4 Pulsed into the reaction chamber with nitrogen at a suitable flow rate, mnSO 4 The Mn content in the alloy is 0.1% of the mass of the matrix, the alloy is adsorbed on the matrix material, the pulse time is adjusted according to the input amount of the matrix material until the air pressure reaches a certain value, and then the alloy is purged by nitrogen with higher flow rate and the rest is taken awayThe nitrogen purge time depends on the volume of the reactor, and then a certain amount of alkali source steam ammonia water is pulsed into the reaction chamber under the carrying of nitrogen with a certain flow rate and chemically adsorbed with MnSO on the substrate material 4 React to form Mn (OH) 2 The time is adjusted according to the input amount of the matrix material, then excessive ammonia water and byproducts are flushed out of the reaction chamber by nitrogen with higher flow rate, the flushing time is adjusted according to the volume of the reactor, then the temperature of the reaction chamber is heated to 500 ℃ for 2 hours under the nitrogen atmosphere, and residual lithium is captured in the ALD deposition heating process, so that a deposited MnO layer and the captured residual lithium form a fast ion conductor layer, and a pre-coated matrix is obtained.
S3, pretreatment of carbon source
Soaking lignite accounting for 1.75% of the mass ratio of the matrix in KH560 liquid converted by Si element accounting for 0.1% of the mass ratio of the matrix, uniformly mixing, and vacuum drying at 50 ℃ for 12 hours to obtain a pretreated carbon source.
S4, premixing PTFE accounting for 0.02% of the lignite of the step S3, PVDF accounting for 10% of the lignite of the step S3 and a pretreated carbon source obtained in the step S3, uniformly mixing the precoated matrix obtained in the step S2 with the premix in a high-speed mixer, putting the mixture into a sagger, putting the sagger into a nitrogen furnace, heating to 260 ℃ at a speed of 3 ℃/min in a nitrogen atmosphere with an oxygen concentration of less than 50ppm, preserving heat for 6 hours, cooling, and mechanically crushing, classifying, sieving and demagnetizing the product in an air environment with a dew point of less than-20 to obtain the high-stability positive electrode lithium supplementing material.
Example 4
The embodiment provides a preparation method of a positive electrode lithium supplementing material, which comprises the following specific steps:
s1, preparing a lithium-rich iron core particle matrix material
Weighing Fe with corresponding weight according to the molar ratio of Li to Fe to Zr=5.2 to 0.88 to 0.12 2 O 3 、Li 2 O、ZrO 2 Mixing in a high-speed mixer, placing the mixture into a sagger, placing into a nitrogen furnace, heating to 750deg.C at a rate of 5deg.C/min in nitrogen atmosphere with oxygen concentration lower than 50ppm, maintaining the temperature for 20h, cooling, and coolingMechanically crushing and grading the product in nitrogen atmosphere to obtain the lithium-rich iron core particle matrix material Li 5.2 Fe 0.88 Zr 0.12 O 4 。
S2, preparing a pre-coated substrate
Placing the lithium-rich iron core particle matrix material obtained in the step S1 into a reaction chamber of an ALD device, vacuumizing, replacing nitrogen, heating the reaction chamber to 60 ℃, maintaining the reaction chamber at a certain pressure, rotating the reactor, and then, carrying out atomic layer deposition on a precursor MgCl 2 Pulsed into the reaction chamber with nitrogen at a suitable flow rate, mgCl 2 The Mg content in the catalyst is 0.05% of the mass ratio of the matrix, the catalyst is adsorbed on the matrix material, the pulse time is adjusted according to the input amount of the matrix material until the air pressure reaches a certain value, then the catalyst is purged with nitrogen with higher flow rate and the residual precursor is taken away, the nitrogen purging time is dependent on the volume of the reactor, and then a certain amount of oxygen source steam H is introduced 2 O 2 Pulse into the reaction chamber under the carrying of nitrogen with a certain flow rate, and chemically adsorb MgCl on the matrix material 2 The reaction is carried out to generate MgO, the time is adjusted according to the input amount of the matrix material, and then excessive H is generated 2 O 2 And the byproducts are flushed out of the reaction chamber by nitrogen with higher flow rate, the flushing time is adjusted according to the volume of the reactor, then the temperature of the reaction chamber is raised to 500 ℃ for 5 hours under the nitrogen atmosphere, and the deposited MgO layer and the captured residual lithium form a fast ion conductor layer due to capturing residual lithium in the ALD deposition heating process, so that the pre-coated substrate is obtained.
S3, pretreatment of carbon source
Soaking bituminous coal accounting for 1.55 percent of the mass of the matrix in KH560 liquid converted by Si element accounting for 0.5 percent of the mass of the matrix, uniformly mixing, and then vacuum drying at 50 ℃ for 12 hours to obtain a pretreated carbon source.
S4, premixing PTFE accounting for 0.15% of the bituminous coal in the step S3, PVDF accounting for 12% of the bituminous coal in the step S3 and a pretreated carbon source obtained in the step S3, uniformly mixing the precoated matrix obtained in the step S2 with the premix in a high-speed mixer, putting the mixture into a sagger, putting the sagger into a nitrogen furnace, heating to 260 ℃ at a speed of 3 ℃/min in a nitrogen atmosphere with an oxygen concentration of less than 50ppm, preserving heat for 6 hours, cooling, and mechanically crushing, classifying, sieving and demagnetizing the product in an air environment with a dew point of less than-20 to obtain the high-stability positive electrode lithium supplementing material.
Example 5
The embodiment provides a preparation method of a positive electrode lithium supplementing material, which comprises the following specific steps:
s1, preparing a lithium-rich iron core particle matrix material
Weighing Fe with corresponding weight according to the molar ratio of Li to Fe to V=5.2 to 0.95 to 0.05 2 O 3 、Li 2 O、V 2 O 5 Mixing uniformly in a high-speed mixer, placing the mixed material into a sagger, placing into a nitrogen furnace, heating to 820 ℃ at a speed of 5 ℃/min in a nitrogen atmosphere with an oxygen concentration of less than 50ppm, preserving heat for 12 hours, cooling, and mechanically crushing and grading the product in the nitrogen atmosphere to obtain the lithium-rich iron-based core particle matrix material Li 5.2 Fe 0.95 V 0.05 O 4 。
S2, preparing a pre-coated substrate
Putting the lithium-rich iron core particle matrix material obtained in the step S1 into a reaction chamber of ALD equipment, vacuumizing, replacing nitrogen, heating the reaction chamber to 120 ℃, maintaining the reaction chamber at a certain pressure, rotating the reactor, gasifying precursor SiO nano liquid for atomic layer deposition, then pulsing the precursor SiO nano liquid into the reaction chamber under the carrying of nitrogen with a proper flow rate, wherein the Si content in SiO accounts for 0.05% of the mass ratio of the matrix and is adsorbed on the matrix material, the pulsing time is adjusted according to the input amount of the matrix material until the air pressure reaches a certain value, then purging with nitrogen with a higher flow rate and taking away the residual precursor, the nitrogen purging time is adjusted according to the volume of the reactor, then heating the reaction chamber to 500 ℃ for 4 hours under the nitrogen atmosphere, and capturing residual lithium in the ALD deposition heating process, so that the deposited SiO layer and the captured residual lithium form a fast ion conductor layer, and the pre-coated matrix is obtained.
S3, pretreatment of carbon source
Immersing starch accounting for 1.55% of the mass ratio of the matrix in KH560 liquid converted by Si element accounting for 0.01% of the mass ratio of the matrix, uniformly mixing, and vacuum drying at 50 ℃ for 12 hours to obtain a pretreated carbon source;
s4, premixing PTFE accounting for 0.08% of the mass ratio of the starch in the step S3, PVDF accounting for 5% of the mass ratio of the starch in the step S3 and a pretreated carbon source obtained in the step S3, uniformly mixing the pre-coated substrate obtained in the step S2 and the premix in a high-speed mixer, putting the mixture into a sagger, putting the sagger into a nitrogen furnace, heating to 200 ℃ at the speed of 3 ℃/min in the nitrogen atmosphere with the oxygen concentration of less than 50ppm, preserving heat for 6 hours, cooling, and mechanically crushing, classifying, sieving and removing magnetism to obtain the high-stability positive electrode lithium supplementing material in the air environment with the dew point of less than-20.
Comparative example 1
Weighing Fe with corresponding weight according to the molar ratio of Li to Fe to Ti=5.1 to 0.99 to 0.01 2 O 3 、Li 2 O、TiO 2 Mixing uniformly in a high-speed mixer, placing the mixed material into a sagger, placing into a nitrogen furnace, heating to 850 ℃ at a speed of 5 ℃/min in a nitrogen atmosphere with an oxygen concentration of less than 50ppm, preserving heat for 15 hours, cooling, and mechanically crushing and grading the product in the nitrogen atmosphere to obtain the conventional uncoated lithium-rich ferrite material Li 5.1 Fe 0.99 Ti 0.01 O 4 。
Experimental test:
1. XRD testing
XRD tests were performed on the positive electrode lithium-supplementing materials prepared in examples 1 to 5 and the conventional uncoated lithium-rich ferrite material prepared in comparative example 1, and XRD test results of the positive electrode lithium-supplementing materials prepared in examples 1 to 5 are shown in FIGS. 1 to 5. As can be seen from FIGS. 1 to 5, examples 1 to 5 and Li 5 FeO 4 Compared with a standard card (PDF # 75-1253), the peak strength and peak position matching degree are higher, and almost no impurity peak exists, so that the positive electrode lithium supplementing material prepared in the embodiment 1-5 has higher crystallinity, and the synthesized sample has high purity and no impurity phase.
2. Electron microscope test
The positive electrode lithium-supplementing material prepared in example 1 was subjected to Scanning Electron Microscope (SEM) test, and the results are shown in fig. 6 to 7. As can be seen from fig. 6, the positive electrode lithium-compensating material prepared in example 1 is round spherical particles, without broken particles or fine powder; as can be seen from fig. 7, the particle surface has a dense and uniform coating, and a higher brightness of the coating indicates better electron conductivity.
Further, transmission Electron Microscope (TEM) tests were performed on the positive electrode lithium-supplementing materials prepared in examples 1 to 5, and as can be seen from fig. 8 to 12, the surface of each single particle of the positive electrode lithium-supplementing materials prepared in examples 1 to 5 is completely wrapped with a coating layer with a distinct interface, and the sheet-shaped carbon is uniformly embedded in the coating layer, so as to play a role of an electron channel.
From the above figures, it can be seen that the positive electrode lithium-supplementing materials prepared in examples 1 to 5 have similar microscopic morphology, generally single-particle crystal or sphere-like morphology, and medium particle size of 1 to 20 micrometers.
3. Electrochemical performance test
The test method is as follows: taking the positive electrode lithium supplementing material prepared in the examples 1-5 and the conventional uncoated lithium-rich ferrite material prepared in the comparative example 1, respectively mixing the materials with acetylene black and polyvinylidene fluoride (PVDF) in a mass ratio of 8:1:1 in a proper amount of N-methylpyrrolidone (NMP) solution, and then coating the mixture on an aluminum foil to prepare a positive plate; the negative electrode sheet adopts a lithium sheet, and is added with a diaphragm and electrolyte, wherein the electrolyte is LiPF of 1mol/L 6 The solution is a mixed solution of EC, DEC and DMC, the volume ratio of EC, DEC and DMC is 1:1:1, and the button cell with model 2032 is assembled in a glove box filled with argon. The test is carried out on a LAND battery tester, the current density is 0.05 ℃, the test voltage range is 2.8V-4.5V, and the test temperature is 25 ℃ at room temperature.
The test results are shown in table 1 below:
TABLE 1 electrochemical Performance test results
The first charge and discharge curves of the materials of example 1 and comparative example 1 are drawn, specifically, as shown in fig. 13, fig. 13 is a first charge and discharge curve of the normal temperature current density 0.05C voltage 2.8V-4.5V of the 2032 button cell made of the positive electrode lithium-supplementing material prepared in example 1 and the conventional uncoated lithium-rich ferrite material of comparative example 1 respectively.
As can be seen from table 1 and fig. 13, the positive electrode lithium supplementing material prepared in the embodiment of the invention has higher first charge and discharge capacity, which indicates that the positive electrode lithium supplementing material has better lithium supplementing effect in the first charging process.
4. Residual alkali test
Residual alkali tests were performed on the positive electrode lithium-supplementing materials prepared in examples 1 to 5 and the conventional uncoated lithium-rich ferrite material prepared in comparative example 1, and the results are shown in table 2.
Residual alkali testing method: adding ultrapure water as residual alkali test solvent, adding a certain proportion of material to be tested, stirring for a certain time until residual alkali is dissolved in water, centrifuging, filtering to obtain filtrate, adding indicator, titrating with hydrochloric acid solution to obtain OH with hydrochloric acid solution consumption of indicator at the color change end point - And CO 3 2- Is calculated according to the content of the (3).
TABLE 2 residual alkali test results
As can be seen from Table 2, the residual alkali of the positive electrode lithium-supplementing materials prepared in examples 1 to 5 is greatly reduced, which is nearly half lower than that of the conventional uncoated lithium-rich ferrite material, wherein the residual alkali OH - The content is obviously reduced, and the residual alkali CO 3 2- And is lower than the uncoated lithium-rich ferrite material, which shows that the surface stability of the positive electrode lithium supplementing materials prepared in examples 1 to 5 is greatly improved.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.
Furthermore, those skilled in the art will appreciate that while some embodiments herein include some features but not others included in other embodiments, combinations of features of different embodiments are meant to be within the scope of the invention and form different embodiments. For example, in the claims below, any of the claimed embodiments may be used in any combination. The information disclosed in this background section is only for enhancement of understanding of the general background of the invention and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person skilled in the art.
Claims (10)
1. The preparation method of the high-stability positive electrode lithium supplementing material is characterized by comprising the following steps of:
(1) Preparing a lithium-rich iron core matrix material;
(2) Depositing coated metal oxide on the surface of the lithium-rich iron core matrix material by ALD, capturing residual lithium in the ALD deposition heating process to form a fast ion conductor layer, and obtaining a pre-coated matrix;
(3) Pretreatment of carbon source: modifying a carbon source by a coupling agent to obtain a pretreated carbon source, wherein the carbon source is a low-temperature easy-carbonization carbon source with carbonization temperature lower than 260 ℃;
(4) Premixing the pretreated carbon source prepared in the step (3) with the organic nano powder in a preset proportion, then carrying out dry-method or wet-method mixed coating on the pretreated carbon source and the pretreated substrate obtained in the step (2), and carrying out heat treatment in an inert atmosphere at the temperature of 60-260 ℃ for 2-24 hours; and crushing, dissociating and grading the material after the heat treatment to obtain the high-stability positive electrode lithium supplementing material.
2. The method for preparing the high-stability positive electrode lithium supplementing material according to claim 1, wherein,
in the step (1), the molecular formula of the lithium-rich iron-based core matrix material is Li x Fe y M z O 4 The method comprises the steps of carrying out a first treatment on the surface of the Wherein Fe is dissociated fromThe son is positive trivalent, x is more than or equal to 4.0 and less than or equal to 6.0,0.85, y is more than or equal to 1.0, z is more than or equal to 0 and less than or equal to 0.15, and z=1-y;
when 0<z is less than or equal to 0.15, M is at least one metal element selected from Co, ni, mn, nb, al, ti, zr, si, cr, V, mo, and the valence state of M metal ions is more than or equal to positive trivalent.
3. The method for preparing the high-stability positive electrode lithium supplementing material according to claim 1, wherein,
in the step (2), the metal element in the ALD deposited metal oxide is at least one of Zn, cr, mn, si, ti, al, mg, ca, W; the ion valence states of the metal elements are the lowest stable valence states except zero valence; the metal element in the metal oxide accounts for 0.02-2% of the mass of the lithium-rich iron core matrix material.
4. The method for preparing the high-stability positive electrode lithium supplementing material according to claim 1, wherein,
in the step (3), the low-temperature easy-carbonization carbon source is one or more of carbohydrate, low-molecular organic matters or petroleum lysate with carbonization temperature lower than 260 ℃.
5. The method for preparing the high-stability positive electrode lithium supplementing material according to claim 1, wherein,
in the step (3), the coupling agent is a silane coupling agent, and the coupling agent is KH560 silane coupling agent.
6. The method for preparing the high-stability positive electrode lithium supplementing material according to claim 1, wherein,
the step of pretreating the carbon source in the step (3) is specifically to dip the carbon source into the coupling agent liquid for uniform mixing or spray the coupling agent liquid into the carbon source for uniform mixing, and then dry for 2-24 hours at the temperature lower than 60 ℃ in the air or vacuum environment.
7. The method for preparing a high-stability positive electrode lithium supplementing material according to claim 5, wherein,
the carbon source accounts for 0.5-10% of the mass of the lithium-rich iron core matrix material; the mass ratio of Si element in the coupling agent to the lithium-rich iron core matrix material is 0.01-0.1%.
8. The method for preparing the high-stability positive electrode lithium supplementing material according to claim 1, wherein,
the organic nano powder in the step (4) comprises PTFE which plays a role of a rigid structure and one or two or more of PVDF, PAN, PMMA which plays a role of hydrophobicity and is soluble in NMP;
the PTFE with the function of rigid structure accounts for 0.01 to 1 percent of the mass of the carbon source; the organic nano powder which plays a role in hydrophobicity and can be dissolved in NMP accounts for 0.01-50% of the carbon source by mass.
9. A high-stability positive electrode lithium supplementing material prepared by the preparation method of any one of claims 1 to 8, which is characterized by comprising a lithium-rich iron core matrix material, a fast ion conductor layer coated on the surface of the lithium-rich iron core matrix material, and an organic-inorganic conductive carbon layer which is coated on the surface of the fast ion conductor layer, can be communicated with an organic-inorganic interface and has a rigid structure and hydrophobicity; the high-stability positive electrode lithium supplementing material is in a single-particle crystal or spheroid shape, and the medium grain diameter is 1-20 microns.
10. A lithium ion battery comprising a positive electrode sheet, wherein the positive electrode slurry for preparing the positive electrode sheet comprises the high-stability positive electrode lithium supplementing material of claim 9.
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