CN115842110A - Negative active material, preparation method thereof, negative pole piece, secondary battery and electric device - Google Patents
Negative active material, preparation method thereof, negative pole piece, secondary battery and electric device Download PDFInfo
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Abstract
The application provides a negative active material, a preparation method thereof, a negative pole piece, a secondary battery and an electric device, wherein the negative active material comprises a core and a coating layer; the coating layer coats at least one part of the surface of the inner core; the inner core is a silicon-oxygen compound, and the coating layer is mesoporous Gamma-Al 2 O 3 . According to the cathode active material, the coating layer absorbs water in the electrolyte, the consumption of active lithium ions and the battery swelling degree are reduced, the first coulombic efficiency, the circulating capacity retention rate and the rate capacity retention rate of the battery are improved, and the stability and the safety of the battery are improved.
Description
Technical Field
The application relates to the technical field of secondary batteries, in particular to a negative active material, a preparation method thereof, a negative pole piece, a secondary battery and an electric device.
Background
In recent years, with the wider application range of secondary batteries, secondary batteries are widely used in energy storage power systems such as hydraulic power, thermal power, wind power, and solar power stations, and in various fields such as electric tools, electric bicycles, electric motorcycles, electric automobiles, military equipment, and aerospace. As the development of secondary batteries has been greatly advanced, higher requirements are also placed on energy density, cycle performance, safety performance, and the like.
The electrolyte of the secondary battery often contains trace moisture, and the trace moisture causes the battery to generate gas including CO in the stages of formation, circulation and high-temperature storage 2 、H 2 CO, hydrocarbon and the like, and the battery drum is caused, so that the use safety is reduced; at the same time, the presence of moisture promotes Li 2 The generation of O increases the consumption of active lithium ions, which leads to the reduction of the first coulombic efficiency of the battery, the capacity attenuation of the battery in the circulating process is enhanced, and the circulating performance is reduced. Therefore, it is highly desirable to improve the safety, first coulombic efficiency, and cycle performance of the battery.
Disclosure of Invention
The present invention has been made in view of the above problems, and an object of the present invention is to provide a negative electrode active material, a method for producing the same, a negative electrode sheet, a secondary battery, and an electric device, which solve the problems of battery swelling and low safety due to a small amount of moisture in an electrolyte, and also solve the problems of increased consumption of active lithium ions due to a small amount of moisture, and further, the first coulomb degradation and cycle performance degradation of the battery.
In order to achieve the above object, a first aspect of the present application provides an anode active material including a core and a coating layer; the coating layer covers at least a part of the surface of the inner core(ii) a The inner core is a silicon-oxygen compound, and the coating layer is mesoporous Gamma-Al 2 O 3 。
Thereby, the mesoporous Gamma-Al in the anode active material 2 O 3 The coating layer is combined with trace moisture in the electrolyte to generate AlOOH, so that the moisture is absorbed, the consumption of active lithium ions is reduced, and the first coulombic efficiency and the circulating capacity retention rate of the battery are improved; furthermore, the r-Al pore in the anode active material 2 O 3 The coating layer absorbs water, so that the gas production rate in the battery is reduced, the battery drum degree is reduced, and the stability and the safety of the battery are improved; meanwhile, the mesoporous Gamma-Al in the anode active material 2 O 3 The coating layer is beneficial to the transmission of lithium ions, so that the battery has excellent rate capacity retention performance.
In any of the embodiments, r-Al 2 O 3 The pore size distribution of (B) is 5nm-50nm, optionally 10nm-30nm. The pore size distribution is favorable for further improving the absorption of the coating layer on trace moisture and further reducing the consumption of active lithium ions, so that the first coulombic efficiency and the cycle performance of the battery are improved, the battery swelling can be further inhibited, and the safety and the stability of the battery are improved; the coating layer with the pore size distribution has good lithium ion transmission performance and high rate capacity retention rate, and is beneficial to exerting the actual specific capacity of the core material.
In any embodiment, the coating has a thickness of 400nm to 1100nm, optionally 500nm to 1000nm. The coating layer is too thick, and occupies too large volume, so that the energy density and the capacity of the battery are easily reduced; the coating layer is too thin to effectively absorb water in the battery, and the consumption of active lithium ions and the degree of swelling of the battery cannot be reduced, so that the battery has low first coulomb efficiency, low cycle capacity retention rate, and low safety and stability.
In any embodiment, the mass ratio of the aluminum element to the silicon element in the anode active material is 1. Thereby improving the mesoporous Gamma-Al of the anode active material 2 O 3 The coating layer absorbs moisture in the battery, the consumption of active lithium ions is further reduced, and the batteryThe first coulombic efficiency and the cycle performance are further improved, and meanwhile, the battery has the advantages of reduced tympanites and further improved safety and stability.
In any embodiment, the inner core is SiO x Wherein x is 1-2; alternatively, x is 1.1 to 1.5. The negative active material adopting the core is beneficial to keeping higher energy density and capacity of the battery.
In any embodiment, the particle size of the inner core is from 1 μm to 20 μm, optionally from 3 μm to 10 μm. The particle size is too small, the proportion of the core material in the anode active material with the same volume is relatively reduced, so that the energy density and the capacity of the battery are reduced; the particle size is too large, which is not beneficial to the formation of a core-shell structure and is easy to cause incomplete coating of a coating layer.
A second aspect of the present application provides a method of preparing an anode active material, comprising the steps of:
(1) Mixing aluminum particles, silicon particles and water to obtain a mixture;
(2) Reacting the mixture at a high temperature in a sealed environment to obtain a reaction product;
(3) And cooling, drying and roasting the reaction product to obtain the cathode active material.
Thus, the present disclosure provides mesoporous r-Al in anode active materials 2 O 3 The coating layer is combined with trace moisture in the electrolyte to generate AlOOH, so that the moisture is absorbed, the consumption of active lithium ions is reduced, and the first coulombic efficiency and the circulating capacity retention rate of the battery are improved; and, the mesoporous Gamma-Al of the anode active material 2 O 3 The coating layer absorbs water, so that the gas production rate in the battery is reduced, the battery drum degree is reduced, and the stability and the safety of the battery are improved; meanwhile, the mesoporous Gamma-Al in the anode active material 2 O 3 The coating layer is beneficial to the transmission of lithium ions, so that the battery has excellent rate capacity retention performance.
In any embodiment, in step (1), the pH of the mixed system is adjusted to 5 to 7, for example, 6, during or after mixing.
In any embodiment, the elevated temperature in step (2) is from 120 ℃ to 200 ℃, optionally from 160 ℃ to 190 ℃, for example 180 ℃.
In any embodiment, in step (2), the reaction is continued for 1 to 6 hours, optionally 2 to 5 hours, for example 3 hours.
In any embodiment, in step (3), the calcination is carried out at 400 ℃ to 800 ℃ (e.g., 600 ℃) for 2 to 6 hours (optionally 3 to 5 hours).
In any embodiment, in step (3), the calcination is performed under the protection of an inert gas (e.g., argon).
In any embodiment, in step (3), the calcination is carried out at a rate of 1 ℃/min to 5 ℃/min (e.g., 3 ℃/min) to 400 ℃ to 800 ℃ (e.g., 600 ℃) and thereafter held at that temperature for 2 to 6 hours (optionally 3 to 5 hours).
In any embodiment, in step (1), the mass ratio of aluminum particles to silicon particles is 1.
In any embodiment, in step (1), the aluminum particles and the silicon particles are both nano-scale particles.
In any embodiment, in step (3), the reaction product is washed after cooling and before drying.
The negative electrode active material of the first aspect of the present application is produced by the method of the second aspect of the present application.
In a third aspect, the present application provides a negative electrode sheet, including the negative electrode active material of the first aspect of the present application or the negative electrode active material prepared by the method of the second aspect of the present application. The negative pole piece can absorb trace moisture in the battery, reduces active lithium ion consumption, improves the first coulombic efficiency and the circulating capacity retention rate of the battery, reduces the battery drum swelling degree, and improves the stability and the safety of the battery.
A fourth aspect of the present application provides a secondary battery comprising the negative active material of the first aspect of the present application, the negative active material prepared by the method of the second aspect of the present application, or the negative electrode tab of the third aspect of the present application.
A fifth aspect of the present application provides an electric device including the secondary battery of the fourth aspect of the present application.
Drawings
Fig. 1 is a schematic view of a secondary battery according to an embodiment of the present application.
Fig. 2 is an exploded view of the secondary battery according to the embodiment of the present application shown in fig. 1.
Fig. 3 is a schematic diagram of an electric device in which a secondary battery according to an embodiment of the present application is used as a power source.
Fig. 4 is an SEM photograph of the negative active material of example 1 of the present application.
Fig. 5 is a TEM photograph of the negative active material of example 1 of the present application.
Fig. 6 is an XRD spectrum of the negative active material of example 1 of the present application.
Fig. 7 is an isothermal adsorption curve of the negative active material of example 1 of the present application.
Fig. 8 is a pore size distribution diagram of a negative active material of example 1 of the present application.
Description of reference numerals:
5 a secondary battery; 51 a housing; 52 an electrode assembly; 53 a cap assembly.
Detailed Description
Hereinafter, embodiments of the negative electrode active material having a core-shell structure, the method for producing the same, the negative electrode sheet, the secondary battery, the battery module, the battery pack, and the electric device according to the present application are specifically disclosed in detail with reference to the drawings as appropriate. But a detailed description thereof will be omitted. For example, detailed descriptions of already known matters and repetitive descriptions of actually the same configurations may be omitted. This is to avoid unnecessarily obscuring the following description, and to facilitate understanding by those skilled in the art. The drawings and the following description are provided for those skilled in the art to fully understand the present application, and are not intended to limit the subject matter recited in the claims.
The "ranges" disclosed herein are defined in terms of lower limits and upper limits, with a given range being defined by a selection of one lower limit and one upper limit that define the boundaries of the particular range. Ranges defined in this manner may or may not include endpoints and may be arbitrarily combined, i.e., any lower limit may be combined with any upper limit to form a range. For example, if ranges of 60-120 and 80-110 are listed for a particular parameter, it is understood that ranges of 60-110 and 80-120 are also contemplated. Furthermore, if the minimum range values 1 and 2 are listed, and if the maximum range values 3,4, and 5 are listed, the following ranges are all contemplated: 1-3, 1-4, 1-5, 2-3, 2-4 and 2-5. In this application, unless otherwise stated, the numerical range "a-b" represents a shorthand representation of any combination of real numbers between a and b, where a and b are both real numbers. For example, a numerical range of "0 to 5" indicates that all real numbers between "0 to 5" have been listed herein, and "0 to 5" is only a shorthand representation of the combination of these numbers. In addition, when a parameter is an integer of 2 or more, it is equivalent to disclose that the parameter is, for example, an integer of 2, 3,4, 5, 6, 7, 8, 9, 10, 11, 12, or the like.
All embodiments and alternative embodiments of the present application may be combined with each other to form new solutions, if not specifically stated.
All technical and optional features of the present application may be combined with each other to form new solutions, if not otherwise specified.
All steps of the present application may be performed sequentially or randomly, preferably sequentially, if not specifically stated. For example, the method comprises steps (a) and (b), meaning that the method may comprise steps (a) and (b) performed sequentially, and may also comprise steps (b) and (a) performed sequentially. For example, reference to the process further comprising step (c) means that step (c) may be added to the process in any order, for example, the process may comprise steps (a), (b) and (c), may also comprise steps (a), (c) and (b), may also comprise steps (c), (a) and (b), etc.
The terms "comprises" and "comprising" as used herein mean either open or closed unless otherwise specified. For example, the terms "comprising" and "comprises" may mean that other components not listed may also be included or included, or that only listed components may be included or included.
In this application, the term "or" is inclusive, if not otherwise specified. For example, the phrase "a or B" means "a, B, or both a and B. More specifically, either of the following conditions satisfies the condition "a or B": a is true (or present) and B is false (or not present); a is false (or not present) and B is true (or present); or both a and B are true (or present).
[ Secondary Battery ]
A secondary battery is also called a rechargeable battery or a secondary battery, and refers to a battery that can be continuously used by activating an active material by means of charging after the battery is discharged.
In general, a secondary battery includes a positive electrode tab, a negative electrode tab, a separator, and an electrolyte. In the process of charging and discharging the battery, active ions (such as lithium ions) are inserted and extracted back and forth between the positive pole piece and the negative pole piece. The isolating membrane is arranged between the positive pole piece and the negative pole piece, mainly plays a role in preventing the short circuit of the positive pole and the negative pole, and can enable active ions to pass through. The electrolyte is arranged between the positive pole piece and the negative pole piece and mainly plays a role in conducting active ions.
Negative electrode active material
One embodiment of the present application provides a negative active material including a core and a coating layer; the coating layer coats at least one part of the surface of the inner core; the inner core is a silicon-oxygen compound, and the coating layer is mesoporous Gamma-Al 2 O 3 。
Although the mechanism is not clear, the applicant has surprisingly found that: at present, trace moisture in the battery can decompose lithium hexafluorophosphate in an electrolyte to generate hydrogen fluoride, the hydrogen fluoride further corrodes lithium carbonate in an SEI film to generate irreversible lithium oxide and carbon dioxide, the consumption of active lithium is increased, and the battery is expanded due to the increase of internal gas, so that the first coulombic efficiency and the cycle capacity retention rate of the battery are reduced, and the safety and the stability are reduced. The application is realized through mesoporous Gamma-Al in a negative active material 2 O 3 The coating layer combines with trace moisture in the battery to generate AlOOH, thereby achieving the purpose of absorbing moisture and blocking the generation of hydrogen fluoride, thereby reducing the content of hydrogen fluorideThe consumption of active lithium ions is reduced, and the first coulombic efficiency and the circulating capacity retention rate of the battery are improved; and, the mesoporous r-Al in the anode active material 2 O 3 The coating layer absorbs water, so that the gas production rate in the battery is reduced, the battery drum degree is reduced, and the stability and the safety of the battery are improved; meanwhile, the mesoporous Gamma-Al in the anode active material 2 O 3 The coating layer is beneficial to the transmission of lithium ions, so that the battery has excellent rate capacity retention performance.
In some embodiments, the mesoporous Gamma-Al 2 O 3 The pore size distribution of (B) is 5nm-50nm, optionally 10nm-30nm, such as 10nm-20nm, 15nm-25nm, and 20nm-30nm. The pore size distribution is favorable for further improving the absorption of the coating layer on trace moisture in the battery and further reducing the consumption of active lithium ions, so that the first coulombic efficiency and the cycle performance of the battery are further improved, the battery swelling can be effectively inhibited, and the safety and the stability of the battery are further improved; the coating layer with the pore size distribution has good lithium ion transmission performance and high rate capacity retention rate, and is favorable for exerting the actual specific capacity of the core material.
In some embodiments, the coating has a thickness of 400nm to 1100nm, optionally 500nm to 1000nm. The coating layer with the thickness can effectively absorb water in the battery, and reduce the consumption of active lithium ions and the swelling degree of the battery, so that the first coulombic efficiency and the circulating capacity retention rate of the battery are improved, the safety and the stability of the battery are improved, and meanwhile, the battery keeps higher energy density and capacity.
In some embodiments, the mass ratio of aluminum element to silicon element in the anode active material is 1. The aluminum element and the silicon element in the negative active material are in the mass ratio range, so that the mesoporous Gamma-Al of the negative active material is improved 2 O 3 The coating layer absorbs water in the battery, the consumption of active lithium ions is further reduced, the first coulombic efficiency and the cycle performance of the battery are further improved, the battery drum expansion is reduced, and the safety and the stability are further improvedAnd (4) increasing.
In some embodiments, the inner core is SiO x Wherein x is 1-2; alternatively, x is 1.1-1.5, e.g., 1.1, 1.15, 1.2, 1.25, 1.3, 1.4. The negative active material adopting the core is beneficial to keeping higher energy density and capacity of the battery.
In some embodiments, the particle size of the inner core is from 1 μm to 20 μm, optionally from 3 μm to 10 μm. The core within the particle size range can ensure that the coating layer coats the core, is beneficial to forming a core-shell structure, and ensures that the battery has higher energy density and capacity.
Method for preparing negative active material
One embodiment of the present application provides a method of preparing an anode active material, including the steps of:
(1) Mixing aluminum particles, silicon particles and water to obtain a mixture;
(2) Reacting the mixture at a high temperature in a sealed environment to obtain a reaction product;
(3) And cooling, drying and roasting the reaction product to obtain the cathode active material.
Thus, the present disclosure provides mesoporous r-Al in anode active materials 2 O 3 The coating layer is combined with trace moisture in the battery to generate AlOOH, so that the moisture is absorbed, the consumption of active lithium ions is reduced, and the first coulombic efficiency and the circulating capacity retention rate of the battery are improved; and, the mesoporous Gamma-Al of the anode active material 2 O 3 The coating layer absorbs water, so that the gas production rate in the battery is reduced, the battery drum degree is reduced, and the stability and the safety of the battery are improved; meanwhile, the mesoporous Gamma-Al in the anode active material 2 O 3 The coating layer is beneficial to the transmission of lithium ions, so that the battery has excellent rate capacity retention performance.
In some embodiments, in step (1), the pH of the mixed system is adjusted to 5 to 7, for example 6, during or after mixing. The suitable pH value is favorable for forming the mesoporous Gamma-Al 2 O 3 The coating layer covers the silicon oxide inner core.
In some embodiments, the elevated temperature in step (2) is from 120 ℃ to 200 ℃, optionally from 160 ℃ to 190 ℃, for example 180 ℃.
In some embodiments, in step (2), the reaction is continued for 1 to 6 hours, optionally 2 to 5 hours, for example 3 hours.
In some embodiments, in step (3), the calcination is carried out at 400 ℃ to 800 ℃ (e.g., 600 ℃) for 2 to 6 hours (optionally 3 to 5 hours).
In some embodiments, in step (3), the calcination is performed under the protection of an inert gas (e.g., argon).
In some embodiments, in step (1), the mass ratio of aluminum particles to silicon particles is 1.
The negative active material with the core-shell structure can be prepared by adopting the reaction conditions, the roasting conditions and the raw material ratio, wherein the inner core is a silicon-oxygen compound, and the coating layer is mesoporous Gamma-Al 2 O 3 (ii) a The coating layer material can absorb water in the battery, reduce the consumption of active lithium ions, improve the first coulombic efficiency and the circulating capacity retention rate of the battery, reduce the bulge of the battery, and the mesoporous Gamma-Al 2 O 3 The coating layer is beneficial to the transmission of lithium ions, and the rate capacity retention performance of the battery is improved.
In some embodiments, in step (3), the firing is carried out at a rate of 1 ℃/min to 5 ℃/min (e.g., 3 ℃/min) to 400 ℃ to 800 ℃ (e.g., 600 ℃) and thereafter held at that temperature for 2 to 6 hours (optionally 3 to 5 hours). The roasting condition is favorable for forming SiO as the kernel x (x is 1-2) and the coating layer is mesoporous Gamma-Al 2 O 3 The negative electrode active material of (1).
In some embodiments, in step (1), the mass of water is 100 to 160 times the sum of the masses of the aluminum particles and the silicon particles.
In some embodiments, in step (1), the aluminum particles and the silicon particles are both nano-scale particles.
In some embodiments, in step (3), the reaction product is washed after cooling and before drying. The washing treatment can keep the purity of the reaction product, avoid the side reaction in the subsequent drying and roasting treatment, and improve the purity of the cathode active material.
In some embodiments, in step (3), the washing with water and ethanol is performed multiple times.
In some embodiments, in step (1), the mixing is performed under ultrasonic conditions.
In some embodiments, in step (1), during or after mixing, the pH of the mixed system is adjusted with an acid solution; at least one selected from the group consisting of a hydrochloric acid solution, an acetic acid solution and a sulfuric acid solution may be optionally used.
In some embodiments, in step (2), the reaction is carried out in an autoclave sealed.
In some embodiments, in step (3), the cooling is natural cooling.
In some embodiments, in step (3), drying is performed in a vacuum environment.
[ negative electrode sheet ]
The negative pole piece comprises a negative pole current collector and a negative pole film layer arranged on at least one surface of the negative pole current collector, wherein the negative pole film layer comprises the negative pole active material or the negative pole active material prepared by the method.
As an example, the negative electrode current collector has two surfaces opposite in its own thickness direction, and the negative electrode film layer is disposed on either or both of the two surfaces opposite to the negative electrode current collector.
In some embodiments, the negative electrode current collector may employ a metal foil or a composite current collector. For example, as the metal foil, copper foil can be used. The composite current collector may include a polymer base layer and a metal layer formed on at least one surface of the polymer base material. The composite current collector may be formed by forming a metal material (copper, copper alloy, nickel alloy, titanium alloy, silver alloy, etc.) on a base material of a polymer material (e.g., a base material of polypropylene (PP), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polystyrene (PS), polyethylene (PE), etc.).
In some embodiments, the above-described anode active material or the anode active material prepared by the above-described method may also be used in combination with an anode active material for a battery, which is well known in the art. As an example, a negative active material for a battery known in the art may include at least one of the following materials: artificial graphite, natural graphite, soft carbon, hard carbon, silicon-based materials, tin-based materials, lithium titanate and the like. The silicon-based material may be selected from at least one of elemental silicon, silicon oxy-compounds, silicon-carbon compounds, silicon-nitrogen compounds, and silicon alloys. The tin-based material may be selected from at least one of elemental tin, tin-oxygen compounds, and tin alloys. However, the present application is not limited to these materials, and other conventional materials known in the art that can be used as a battery negative active material may also be used.
In some embodiments, the anode film layer further optionally includes a binder. As an example, the binder may be selected from at least one of Styrene Butadiene Rubber (SBR), polyacrylic acid (PAA), sodium Polyacrylate (PAAs), polyacrylamide (PAM), polyvinyl alcohol (PVA), sodium Alginate (SA), polymethacrylic acid (PMAA), and carboxymethyl chitosan (CMCS).
In some embodiments, the negative electrode film layer further optionally includes a conductive agent. As an example, the conductive agent may be selected from at least one of superconducting carbon, acetylene black, carbon black, ketjen black, carbon dots, carbon nanotubes, graphene, and carbon nanofibers.
In some embodiments, the negative electrode film layer may also optionally include other adjuvants, such as thickeners (e.g., sodium carboxymethyl cellulose (CMC-Na)), and the like.
In some embodiments, the negative electrode sheet can be prepared by: dispersing the components for preparing the negative electrode plate, such as a negative electrode active material, a conductive agent, a binder and any other components, in a solvent (such as deionized water) to form negative electrode slurry; and coating the negative electrode slurry on a negative electrode current collector, and drying, cold pressing and the like to obtain the negative electrode pole piece.
[ Positive electrode sheet ]
The positive electrode sheet generally includes a positive electrode current collector and a positive electrode film layer disposed on at least one surface of the positive electrode current collector, and the positive electrode film layer includes a positive electrode active material.
As an example, the positive electrode current collector has two surfaces opposite in its own thickness direction, and the positive electrode film layer is disposed on either or both of the two surfaces opposite to the positive electrode current collector.
In some embodiments, the positive electrode current collector may employ a metal foil or a composite current collector. For example, as the metal foil, aluminum foil may be used. The composite current collector may include a polymer material base layer and a metal layer formed on at least one surface of the polymer material base layer. The composite current collector may be formed by forming a metal material (aluminum, aluminum alloy, nickel alloy, titanium alloy, silver alloy, etc.) on a base material of a polymer material (e.g., a base material of polypropylene (PP), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polystyrene (PS), polyethylene (PE), etc.).
In some embodiments, the positive active material may employ a positive active material for a battery, which is well known in the art. As an example, the positive electrode active material may include at least one of the following materials: lithium-containing phosphates of olivine structure, lithium transition metal oxides and their respective modified compounds. However, the present application is not limited to these materials, and other conventional materials that can be used as a positive electrode active material of a battery may be used. These positive electrode active materials may be used alone or in combination of two or more. Among them, examples of the lithium transition metal oxide may include, but are not limited to, lithium cobalt oxide (e.g., liCoO) 2 ) Lithium nickel oxides (e.g., liNiO) 2 ) Lithium manganese oxide (e.g., liMnO) 2 、LiMn 2 O 4 ) Lithium nickel cobalt oxide, lithium manganese cobalt oxide, lithium nickel manganese oxide, lithium nickel cobalt manganese oxide (e.g., liNi) 1/3 Co 1/3 Mn 1/3 O 2 (may also be abbreviated as NCM) 333 )、LiNi 0.5 Co 0.2 Mn 0.3 O 2 (may also be abbreviated as NCM) 523 )、LiNi 0.5 Co 0.25 Mn 0.25 O 2 (may also be abbreviated as NCM) 211 )、LiNi 0.6 Co 0.2 Mn 0.2 O 2 (may also be abbreviated as NCM) 622 )、LiNi 0.8 Co 0.1 Mn 0.1 O 2 (may also be abbreviated as NCM) 811 ) Lithium nickel cobalt aluminum oxides (e.g., liNi) 0.85 Co 0.15 Al 0.05 O 2 ) And modified compounds thereof, and the like. Examples of olivine structured lithium-containing phosphates may include, but are not limited to, lithium iron phosphate (e.g., liFePO) 4 (also referred to as LFP for short)), a composite material of lithium iron phosphate and carbon, and lithium manganese phosphate (e.g., liMnPO) 4 ) At least one of a composite material of lithium manganese phosphate and carbon, lithium iron manganese phosphate, and a composite material of lithium iron manganese phosphate and carbon.
In some embodiments, the positive electrode film layer further optionally includes a binder. As an example, the binder may include at least one of polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), vinylidene fluoride-tetrafluoroethylene-propylene terpolymer, vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene terpolymer, tetrafluoroethylene-hexafluoropropylene copolymer, and fluoroacrylate resin.
In some embodiments, the positive electrode film layer further optionally includes a conductive agent. As an example, the conductive agent may include at least one of superconducting carbon, acetylene black, carbon black, ketjen black, carbon dots, carbon nanotubes, graphene, and carbon nanofibers.
In some embodiments, the positive electrode sheet may be prepared by: dispersing the above components for preparing the positive electrode sheet, such as the positive active material, the conductive agent, the binder and any other components, in a solvent (such as N-methylpyrrolidone) to form a positive electrode slurry; and coating the positive electrode slurry on a positive electrode current collector, and drying, cold pressing and the like to obtain the positive electrode piece.
[ electrolyte ]
The electrolyte plays a role in conducting ions between the positive pole piece and the negative pole piece. The kind of the electrolyte is not particularly limited and may be selected as desired. For example, the electrolyte may be liquid, gel, or all solid.
In some embodiments, the electrolyte is liquid and includes an electrolyte salt and a solvent.
In some embodiments, the electrolyte salt may be selected from at least one of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate, lithium hexafluoroarsenate, lithium bis-fluorosulfonylimide, lithium bis-trifluoromethanesulfonylimide, lithium trifluoromethanesulfonate, lithium difluorophosphate, lithium difluorooxalato borate, lithium dioxaoxalato borate, lithium difluorodioxaoxalato phosphate, and lithium tetrafluorooxalato phosphate.
In some embodiments, the solvent may be selected from at least one of ethylene carbonate, propylene carbonate, ethyl methyl carbonate, diethyl carbonate, dimethyl carbonate, dipropyl carbonate, methyl propyl carbonate, ethyl propyl carbonate, butylene carbonate, fluoroethylene carbonate, methyl formate, methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, propyl propionate, methyl butyrate, ethyl butyrate, 1, 4-butyrolactone, sulfolane, dimethylsulfone, methylethylsulfone, and diethylsulfone.
In some embodiments, the electrolyte further optionally includes an additive. By way of example, the additives may include a negative electrode film forming additive, a positive electrode film forming additive, and may further include additives capable of improving certain properties of the battery, such as additives that improve the overcharge properties of the battery, additives that improve the high-or low-temperature properties of the battery, and the like.
[ isolation film ]
In some embodiments, a separator is further included in the secondary battery. The type of the separator is not particularly limited, and any known separator having a porous structure and good chemical and mechanical stability may be used.
In some embodiments, the material of the isolation film may be at least one selected from glass fiber, non-woven fabric, polyethylene, polypropylene and polyvinylidene fluoride. The separator may be a single-layer film or a multilayer composite film, and is not particularly limited. When the separator is a multilayer composite film, the materials of the respective layers may be the same or different, and are not particularly limited.
In some embodiments, the positive electrode tab, the negative electrode tab, and the separator may be manufactured into an electrode assembly through a winding process or a lamination process.
In some embodiments, the secondary battery may include an exterior package. The exterior package may be used to enclose the electrode assembly and electrolyte.
In some embodiments, the outer package of the secondary battery may be a hard case, such as a hard plastic case, an aluminum case, a steel case, or the like. The outer package of the secondary battery may also be a pouch, such as a pouch-type pouch. The material of the soft bag may be plastic, and examples of the plastic include polypropylene, polybutylene terephthalate, polybutylene succinate, and the like.
The shape of the secondary battery is not particularly limited, and may be a cylindrical shape, a square shape, or any other shape. For example, fig. 1 is a secondary battery 5 of a square structure as an example.
In some embodiments, referring to fig. 2, the overwrap may include a housing 51 and a cover plate 53. The housing 51 may include a bottom plate and a side plate connected to the bottom plate, and the bottom plate and the side plate enclose to form an accommodating cavity. The housing 51 has an opening communicating with the accommodation chamber, and a cover plate 53 can cover the opening to close the accommodation chamber. The positive electrode tab, the negative electrode tab, and the separator may be formed into the electrode assembly 52 through a winding process or a lamination process. The electrode assembly 52 is enclosed within the receiving cavity. The electrolyte wets the electrode assembly 52. The number of electrode assemblies 52 contained in the secondary battery 5 may be one or more, and those skilled in the art can select them according to the actual needs.
In some embodiments, the secondary batteries may be assembled into a battery module, and the number of the secondary batteries contained in the battery module may be one or more, and the specific number may be selected by those skilled in the art according to the application and capacity of the battery module.
In some embodiments, the battery modules may be assembled into a battery pack, and the number of the battery modules contained in the battery pack may be one or more, and the specific number may be selected by one skilled in the art according to the application and the capacity of the battery pack.
In addition, this application still provides an electric installation, and electric installation includes the secondary battery that this application provided. The secondary battery may be used as a power source for an electric device, or may be used as an energy storage unit for an electric device. The powered device may include a mobile device (e.g., a mobile phone, a laptop computer, etc.), an electric vehicle (e.g., a pure electric vehicle, a hybrid electric vehicle, a plug-in hybrid electric vehicle, an electric bicycle, an electric scooter, an electric golf cart, an electric truck, etc.), an electric train, a ship, and a satellite, an energy storage system, etc., but is not limited thereto.
As the electricity-using device, a secondary battery, a battery module, or a battery pack may be selected according to its use requirement.
Fig. 3 is an electric device as an example. The electric device is a pure electric vehicle, a hybrid electric vehicle or a plug-in hybrid electric vehicle and the like. In order to meet the demand of the electric device for high power and high energy density of the secondary battery, a battery pack or a battery module may be used.
[ examples ]
Hereinafter, examples of the present application will be described. The following description of the embodiments is merely exemplary in nature and is in no way intended to limit the present disclosure. The examples, where specific techniques or conditions are not indicated, are to be construed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
Example 1
1. Preparation of negative active material: dispersing 0.2g of aluminum nano powder and 0.1g of silicon nano powder into 40ml of deionized water, adjusting the pH value to 6 by hydrochloric acid, and carrying out ultrasonic treatment to obtain a mixture; and transferring the mixture into a stainless steel autoclave with a polytetrafluoroethylene lining, sealing, reacting at 180 ℃ for 3h, naturally cooling, centrifuging and washing with deionized water and ethanol for several times, drying in a vacuum environment, heating to 600 ℃ at a heating rate of 3 ℃/min under the protection of argon, keeping at 600 ℃ for 4h, and roasting to obtain the cathode active material, wherein the SEM photograph of the cathode active material is shown in figure 4.
2. Preparing a negative pole piece: adding a negative electrode active material, a conductive agent carbon black and a binder polyacrylic acid into solvent deionized water according to the weight ratio of 7; and uniformly coating the negative electrode slurry on the copper foil of the negative current collector for one time or multiple times, and drying, cold pressing and slitting to obtain the negative electrode pole piece.
3. Preparing a positive pole piece: lithium iron phosphate (LiFePO) 4 ) Dissolving a material, a conductive agent carbon black and sodium cellulose in a solvent N-methyl pyrrolidone (NMP) according to a weight ratio of 8; and then uniformly coating the positive electrode slurry on a positive electrode current collector aluminum foil, and then drying, cold pressing and cutting to obtain the positive electrode piece.
4. And (3) isolation film: a polypropylene film is used.
5. Preparing an electrolyte: in an argon atmosphere glove box (H) 2 O<0.1ppm，O 2 <0.1 ppm), mixing an organic solvent of Ethylene Carbonate (EC) and Ethyl Methyl Carbonate (EMC) uniformly according to a volume ratio of 3 6 The lithium salt is dissolved in the organic solvent and stirred uniformly.
6. Preparation of secondary battery: stacking and winding the positive pole piece, the isolating membrane and the negative pole piece in sequence to obtain an electrode assembly; and (3) putting the electrode assembly into an outer package, adding the prepared electrolyte, and carrying out processes of packaging, standing, formation, aging and the like to obtain the secondary battery.
Examples 2 to 7 and comparative examples 1 to 3
Examples 2 to 7 and comparative examples 1 to 3 were prepared similarly to the secondary battery of example 1, but parameters of the negative active material were adjusted, and the different parameters are detailed in table 1.
(1) Determination of SiO as core Material in negative active materials of examples 1 to 7 and comparative examples 1 to 3 x The value of (2).
The determination method comprises the following steps: weighing a certain mass of dried negative active material (the mass is recorded as W), placing the dried negative active material into a thermogravimetric/differential thermal analyzer, raising the temperature from room temperature to 1200 ℃ under the air atmosphere, and recording the mass increase (delta W, the mass increase is due to SiO x Is completely oxidized to SiO 2 ) SiO was calculated by combining the mass ratio (z) of Al and Si elements in the raw material according to the following formula x Molar mass of (2) and further calculating SiO x The value of x in (1).
Wherein W is the mass of the dried negative electrode active material, M SiO2 Is the molar mass of silica, M Al Is the molar mass of aluminum, z is the mass ratio of Al to Si elements,. DELTA.W is the mass increment, M Si Is the molar mass of silicon, M Al2O3 Is the molar mass of alumina.
(2) TEM analysis was performed on the negative active materials of examples 1 to 7 and comparative examples 1 to 3, and SiO as a core was obtained from TEM photographs of the negative active materials x Particle size of (a) and thickness of the coating layer; in example 1, a TEM photograph of the negative electrode active material is shown in fig. 5, and SiO on the core is obtained x The grain diameter of the coating is 3-10 μm, and the thickness of the coating is 500-1000 nm.
(3) XRD spectra of the negative active materials of examples 1 to 7 and comparative examples 1 to 3 were measured, and the material of the clad layer was determined by comparing with a standard spectrum; wherein, the XRD spectrum of the cathode active material of the example 1 is shown in figure 6.
(4) The pore size distribution and the porosity of the solid material are measured according to the national standard GB/T21650-2008 mercury intrusion method and a gas adsorption method part 2: analysis of mesopores and macropores by gas adsorption method, pore size distributions of the anode active materials of examples 1 to 7 and comparative examples 1 to 3 were calculated by BJH method, wherein fig. 7 is an isothermal adsorption curve of the anode active material of example 1, and fig. 8 is a pore size distribution diagram of the anode active material of example 1.
The above results are shown in Table 1.
Table 1: parameter results for examples 1-7 and comparative examples 1-3
* Dispersing 0.2g of aluminum nano powder and 0.1g of silicon nano powder into 40ml of deionized water, carrying out ultrasonic treatment to obtain a mixture, centrifuging and washing the mixture by using the deionized water and ethanol for a plurality of times, drying the mixture in a vacuum environment, heating the mixture to 600 ℃ at a heating rate of 3 ℃/min under the protection of argon and normal pressure, keeping the temperature at 600 ℃ for 4 hours, and roasting the mixture to obtain a negative electrode active material to obtain the SiO coated by the non-mesoporous common alumina x And (3) a negative electrode material.
Dispersing 0.2g of aluminum nano powder and 0.1g of silicon nano powder into 40ml of deionized water, adjusting the pH value to 6 by hydrochloric acid, carrying out ultrasonic treatment, reacting for 3 hours at 180 ℃ under normal pressure and in an air atmosphere, naturally cooling, centrifuging and washing by deionized water and ethanol for several times, drying under a vacuum environment, heating to 600 ℃ at a heating rate of 3 ℃/min under the protection of argon, keeping for 4 hours at 600 ℃ for roasting to obtain non-mesoporous Gamma-Al 2 O 3 Coated SiO x Negative polarity material.
Battery testing
The secondary batteries of examples 1 to 7 and comparative examples 1 to 3 were subjected to the following tests.
(1) Normal temperature capacity performance: charging and discharging for the first time at 25 deg.C, constant current and constant voltage charging at 0.33C until the upper limit voltage is 2.00V, constant current discharging at 0.33C until the final voltage is 0.05V, and recording the discharge capacity value as capacity C at normal temperature n 。
(2) Normal temperature cycle performance: charging and discharging for the first time in an environment of 25 ℃, carrying out constant current and constant voltage charging under a charging current of 0.33 ℃ until the upper limit voltage is 2.00V, then carrying out constant current discharging under a discharging current of 1C until the final voltage is 0.05V, and recording the discharging capacity of the first cycle; then, cycling for N times according to the operation, and finally recording the discharge capacity of the Nth cycle; calculating the cycle capacity retention rate according to the following formula; the number of cycles N in this test was 1000.
Cycle capacity retention =100% × (discharge capacity at N-th cycle/discharge capacity at first cycle)
(3) Rate capability: charging and discharging for the first time at 25 ℃, carrying out constant current and constant voltage charging under the charging current of 1/3C until the upper limit voltage is 2.00V, then carrying out constant current discharging under the discharging current of 1/3C, 1C and 3C respectively until the final voltage is 0.05V, and recording each discharging capacity; the percentage of discharge capacity at 1C and 3C discharge current to discharge capacity at 1/3C discharge current was calculated as percentage of rate capacity retention, taking the discharge capacity at 1/3C discharge current as 100%.
The results are shown in Table 2.
Table 2: results of Performance test of the secondary batteries of examples 1 to 7 and comparative examples 1 to 3
As shown in table 2, compared with comparative examples 1 to 3, the normal temperature capacity retention rate, and the rate capacity retention rate of the secondary battery of the present application are all significantly improved, which indicates that the mesoporous r-Al of the anode active material of the present application 2 O 3 The binding capacity of the coating layer and the moisture in the electrolyte is strong, the generation of hydrogen fluoride is blocked, the consumption of active lithium ions is reduced, the normal-temperature capacity and the capacity retention rate are obviously improved, meanwhile, the coating layer structure cannot block the transmission of the lithium ions, and the excellent rate capacity retention performance is presented. The negative active material of the comparative example 1 does not have a coating layer and cannot absorb moisture in the electrolyte, so that a large amount of active lithium ions are consumed, and the normal-temperature capacity, the capacity retention rate and the rate capacity retention performance of the battery are poor; the coating layers of the negative active materials of comparative examples 2 to 3 have weak absorption capacity for moisture and have an effect of inhibiting lithium ion transmission, thereby resulting in low normal temperature capacity, capacity retention rate and rate capacity retention performance of the battery.
The present application is not limited to the above embodiments. The above embodiments are merely examples, and embodiments having substantially the same configuration as the technical idea and exhibiting the same operation and effect within the technical scope of the present application are all included in the technical scope of the present application. In addition, various modifications that can be conceived by those skilled in the art are applied to the embodiments and other embodiments are also included in the scope of the present application, in which some of the constituent elements in the embodiments are combined and constructed, without departing from the scope of the present application.
Claims (16)
1. A negative active material includes a core and a coating layer;
the coating layer coats at least one part of the surface of the inner core;
the inner core is a silicon-oxygen compound, and the coating layer is mesoporous Gamma-Al 2 O 3 。
2. The anode active material of claim 1, wherein the mesoporous r-Al 2 O 3 The pore size distribution of (B) is 5nm-50nm, optionally 10nm-30nm.
3. The negative electrode active material of claim 1 or 2, wherein the coating layer has a thickness of 400nm to 1100nm, optionally 500nm to 1000nm.
4. The anode active material according to any one of claims 1 to 3, wherein a mass ratio of an aluminum element to a silicon element in the anode active material is 1.
5. The negative electrode active material according to any one of claims 1 to 4, wherein the inner core is SiO x Wherein x is 1-2.
6. The negative electrode active material according to any one of claims 1 to 5, wherein the particle size of the inner core is 1 μm to 20 μm.
7. A method of preparing an anode active material, comprising the steps of:
(1) Mixing aluminum particles, silicon particles and water to obtain a mixture;
(2) Reacting the mixture at a high temperature in a sealed environment to obtain a reaction product;
(3) And cooling, drying and roasting the reaction product to obtain the cathode active material.
8. The method according to claim 7, wherein in the step (1), the pH of the mixed system is adjusted to 5 to 7 during or after the mixing.
9. The method according to claim 7 or 8, wherein, in the step (2), the high temperature is 120-200 ℃; alternatively, the reaction is continued for 1 to 6 hours.
10. The method according to any one of claims 7 to 9, wherein, in the step (3), the calcination is carried out at 400 ℃ to 800 ℃ for 2 to 6 hours;
optionally, roasting under the protection of inert gas;
optionally, during roasting, the temperature is raised to 400-800 ℃ at the rate of 1-5 ℃/min, and then the temperature is kept for 2-6 hours.
11. The method according to any one of claims 7 to 10, wherein in step (1), the mass ratio of the aluminum particles to the silicon particles is 1.
12. The method according to any one of claims 7 to 11, wherein in step (1), the aluminum particles and the silicon particles are both nano-scale particles.
13. The process according to any one of claims 7 to 12, wherein in step (3), the cooled reaction product is washed after cooling and before drying.
14. A negative electrode sheet comprising the negative electrode active material of any one of claims 1 to 6 or the negative electrode active material prepared by the method of any one of claims 7 to 13.
15. A secondary battery comprising the negative active material of any one of claims 1 to 6, the negative active material prepared by the method of any one of claims 7 to 13, or the negative electrode tab of claim 14.
16. An electric device comprising the secondary battery according to claim 15.
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| CN116526069A (en) * | 2023-07-04 | 2023-08-01 | 宁德时代新能源科技股份有限公司 | Separator, battery cell, battery and electricity utilization device |
| CN116526069B (en) * | 2023-07-04 | 2023-09-15 | 宁德时代新能源科技股份有限公司 | Separator, battery cell, battery and electricity utilization device |
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