CN114400321A - Low-temperature charge-discharge lithium ion battery and negative electrode material thereof - Google Patents
Low-temperature charge-discharge lithium ion battery and negative electrode material thereof Download PDFInfo
- Publication number
- CN114400321A CN114400321A CN202210151180.8A CN202210151180A CN114400321A CN 114400321 A CN114400321 A CN 114400321A CN 202210151180 A CN202210151180 A CN 202210151180A CN 114400321 A CN114400321 A CN 114400321A
- Authority
- CN
- China
- Prior art keywords
- lithium
- lithium ion
- ion battery
- low
- negative electrode
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—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
- H01M4/581—Chalcogenides or intercalation compounds thereof
- H01M4/5815—Sulfides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
-
- 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
- H01M2004/027—Negative electrodes
Abstract
The invention discloses a low-temperature charge-discharge lithium ion battery and a negative electrode material thereof, wherein a copper-based sulfide Cu is usedxS (x is more than or equal to 1 and less than or equal to 2) is used as a cathode material of the low-temperature lithium ion battery, the material is used as a cathode, and a nickel-cobalt-manganese (NCM) ternary material, a nickel-cobalt-aluminum (NCA) ternary material and lithium iron phosphate (LiFePO) are used4) Material, lithium cobaltate (LiCoO)2) Material, lithium manganate (LiMn)2O4) One of the materials is used as a positive electrode, and the materials are matched to form the lithium ion full cell. The copper-based sulfide related to the negative electrode material can be charged and discharged at constant current under the low-temperature condition of-60 ℃, and provides specific capacity of 182mAh/g, which is equivalent to 52% of capacity at 25 ℃; and has a higher working voltage (1.8)V vs Li+Li), no risk of lithium precipitation during low-temperature charging and discharging, and the constant-current charging and discharging cycle life at-60 ℃ is more than 60 times, thereby providing guarantee for safe and stable charging and discharging of the lithium ion battery under the extreme low-temperature condition.
Description
Technical Field
The invention relates to the field of lithium ion batteries, in particular to a lithium ion battery capable of being charged and discharged at a low temperature of (-60 ℃) and a preparation method of a negative electrode material thereof.
Background
Since the lithium ion battery has the advantages of high voltage, high energy density, long cycle life and the like, the lithium ion battery is widely applied to the fields of portable electronic equipment, new energy automobiles and the like. Currently, the application of lithium ion batteries is gradually expanding to the fields such as deep sea exploration, polar scientific research, national defense military industry, aerospace and the like, and the application scenes have higher requirements on the low-temperature charging and discharging performance of the lithium ion batteries, for example, the deep sea exploration requires that the lithium ion batteries can normally work at the temperature of-40 ℃, and the aerospace field further requires a harsher temperature of-80 ℃. The ideal working temperature range of the current lithium ion battery is about 15-35 ℃, and when the temperature is lower than 0 ℃, the capacity, power and service life of the battery can be greatly attenuated.
At present, the working mode of the lithium ion battery at low temperature is mostly normal temperature charging-low temperature discharging, or the lithium ion battery is heated by combining a thermal management system at low temperature when being charged, and the low temperature (less than or equal to minus 20 ℃) charging is always a bottleneck which is not easy to break through. At present, most of commercial lithium ion batteries use graphite as a negative electrode material, and the main problems existing in the process of charging at low temperature are as follows: the viscosity of the electrolyte is increased and even solidified at low temperature, and the wettability of the electrolyte and an electrode material is poor; the ionic conductivity of the electrolyte is reduced at low temperature; li at Low temperature+Difficulty in desolvation process; the working voltage of the graphite negative electrode is close to that of lithium metal (<0.2V vs Li+Li), graphite polarization is increased at low temperature, lithium is easy to be separated out during charging to form lithium dendrite, the service life of the battery is influenced, and potential safety hazards are brought; li at Low temperature+The migration rate in the electrode material decreases drastically. At present, a commercial lithium ion battery taking graphite as a negative electrode has very low specific charge capacity at low temperature (less than or equal to-20 ℃) and is easy to separate lithium, so that the problems of short cycle life and safety are caused, and the use requirements of special application scenes such as polar scientific research, aerospace and the like on low-temperature charge and discharge of the lithium ion battery cannot be met, so that the development of an electrode material capable of safely and quickly charging and discharging at low temperature is urgently needed.
Currently, the technical means for improving the low-temperature charge and discharge performance of the lithium ion battery are mainly classified into four categories: first, the temperature at which the battery is charged is increased by an internal or external heating strategy, but this approach results in additional energy loss and increases the inactivity of the systemThe nature of the mass, thereby reducing the output energy efficiency of the battery and increasing the complexity and cost of the system; secondly, the structure of the graphite negative electrode is improved, for example, porous graphite is used, the particle size of the graphite is reduced, and the like, so as to improve the charge-discharge kinetics of the graphite negative electrode at a low temperature, and the strategy can improve the charge-discharge performance of the graphite negative electrode at the low temperature to a certain extent, but is limited by the lower working voltage of the graphite, so that the problem that the graphite negative electrode is easy to separate lithium during low-temperature charging cannot be solved; thirdly, an electrolyte solvent or additive with low melting point and low viscosity is used for reducing the viscosity and the melting point of the electrolyte at low temperature and improving the wettability of the electrolyte and an electrode material, and similar to the second strategy, the method can improve the charge and discharge performance of the graphite cathode at low temperature, but still cannot avoid the problem of lithium precipitation during low-temperature charging of the graphite cathode; fourth, use of higher voltage negative electrode materials, such as lithium titanate Li4Ti5O12(working Voltage 1.6V vs. Li/Li)+) The method can prevent the phenomenon of lithium precipitation of the negative electrode during low-temperature charging, but due to Li at low temperature+The diffusion rate in the electrode material is rapidly reduced, so that the voltage polarization of the electrode material is larger during low-temperature charging and discharging, the specific capacity is reduced more than that of the electrode material at normal temperature, and the energy density and the charging and discharging energy efficiency of the lithium ion battery at low temperature are seriously influenced. Therefore, the development of an electrode material which does not precipitate lithium during low-temperature charge and discharge and has higher capacity retention rate than normal-temperature charge and discharge has important practical application significance.
Disclosure of Invention
The invention aims to solve the technical problems that the conventional lithium ion battery cathode material has poor charge-discharge kinetics at low temperature, low specific capacity, lithium precipitation risk in low-temperature charge-discharge and the like. In order to solve the technical problem, the invention provides the use of copper-based sulfide CuxS (x is more than or equal to 1 and less than or equal to 2) is used as a negative electrode material of the low-temperature lithium ion battery, and the material has the advantages of abundant reserves, low cost, environmental friendliness and the like. In addition, the copper-based sulfide has good electronic conductivity, and the material can realize the rapid replacement reaction of Cu ions and Li ions in the charge and discharge process by combining the rapid mobility of the Cu ions, so that the material has very rapid charge and discharge kinetic characteristics.Meanwhile, the material has higher working voltage and no risk of lithium precipitation during low-temperature charging and discharging. Finally, the electrolyte provided by the invention has the advantages of low freezing point, small viscosity at low temperature, high conductivity and the like, and the problems of low-temperature solidification, viscosity increase, ion conductivity reduction and the like of the traditional commercial lithium ion battery electrolyte are solved. The above characteristics make CuxThe lithium metal half-cell with S as the electrode can be charged and discharged at-60 ℃, and shows a specific capacity of 182mAh/g, which is equivalent to 52% of the capacity at 25 ℃. The material is taken as a negative electrode, and a nickel-cobalt-manganese (NCM) ternary material, a nickel-cobalt-aluminum (NCA) ternary material and lithium iron phosphate (LiFePO) are taken4) Material, lithium cobaltate (LiCoO)2) Material, lithium manganate (LiMn)2O4) One of the materials is used as a positive electrode, and the lithium ion full cell is matched with the positive electrode to form the lithium ion full cell, and can still maintain 43.75 percent of capacity at 25 ℃ under the conditions of-40 ℃ and the charge-discharge current density of 15mA/g (0.1C). The invention relates to a specific technical scheme as follows:
the negative electrode material for the low-temperature charge-discharge lithium ion battery comprises a negative electrode active material, a conductive agent and a binder, wherein the negative electrode active material is copper-based sulfide CuxS, x is more than or equal to 1 and less than or equal to 2, and CuxS can be commercial CuS or Cu2S, or copper-based sulfide Cu which is obtained by simply grinding and mixing copper powder and sulfur powder in different proportions and then reacting in N-methyl pyrrolidone solution at 100 ℃ or synthesized by other synthesis methodsxS (1. ltoreq. x. ltoreq.2), which is not limited herein. The CuxThe mass ratio of S is 70-95 wt.%, and the total mass ratio of the conductive agent and the adhesive is 30-5 wt.%; the sum of the mass ratios of the negative electrode active material, the conductive agent and the binder is 1; the loading amount of the negative active material is 1mg/cm2～5mg/cm2。
A low-temperature charge-discharge lithium ion battery comprises a negative pole piece, a positive pole piece, electrolyte and a diaphragm; the negative active material of the negative pole piece is copper-based sulfide CuxS, 1 is more than or equal to x is less than or equal to 2, and the positive active material of the positive pole piece is a nickel-cobalt-manganese (NCM) ternary material, a nickel-cobalt-aluminum (NCA) ternary material and lithium iron phosphate (LiFePO)4) Wood materialMaterial, lithium cobaltate (LiCoO)2) Material, lithium manganate (LiMn)2O4) In one material, the electrolyte comprises lithium salt and solvent, and the positive pole piece and the negative pole piece are separated by a diaphragm.
Further, the CuxThe mass ratio of S is 70-95 wt.%; the negative pole piece further comprises a conductive agent and a binder, wherein the total mass ratio of the conductive agent to the binder is 30-5 wt.%; the loading amount of the negative active material is 1mg/cm2～5mg/cm2。
Furthermore, the binder of the negative electrode plate is one of polyvinylidene fluoride (PVDF), Polytetrafluoroethylene (PTFE), polyvinyl alcohol (PVA), sodium carboxymethylcellulose (CMC) and sodium alginate, and the current collector of the negative electrode plate is one of aluminum foil or copper foil.
Further, the mass ratio of the positive electrode active material is 70-95 wt.%; the positive pole piece further comprises a conductive agent and a binder, the mass ratio of the conductive agent to the binder is 30-5 wt.%, and the sum of the mass ratios of the positive active material, the conductive agent and the binder is 1; the loading amount of the positive active material is 2mg/cm2～10mg/cm2。
Further, the binder of the positive electrode plate is one of polyvinylidene fluoride (PVDF) and Polytetrafluoroethylene (PTFE), and the current collector of the positive electrode plate is an aluminum foil.
Further, the conductive agent of the positive pole piece and the negative pole piece is one or more of acetylene black, ketjen black, carbon nano tubes and graphene.
Further, the capacity ratio of the negative pole piece to the positive pole piece is 1.1: 1-1.2: 1.
Further, the electrolyte solvent is one or more of 1, 3-Dioxolane (DOL), ethylene glycol dimethyl ether (DME), diethylene glycol dimethyl ether (DEGDME), triethylene glycol dimethyl ether (TEGDME) and tetraethylene glycol dimethyl ether (Tetraglyme), and the lithium salt of the electrolyte is lithium hexafluorophosphate (LiPF)6) Lithium bis (fluorosulfonylimide) (LiFSI), lithium trifluoromethanesulfonate (LiCF)3SO3) Lithium bistrifluoromethanesulfonimide (LiTFSI),Lithium perchlorate (LiClO)4) Lithium tetrafluoroborate (LiBF)4) One or more of lithium bis (oxalato) borate (LiBOB) and lithium difluoro (oxalato) borate (LiDFOB), wherein the concentration of the lithium salt is 0.5-3 mol/L.
Further, the diaphragm is one of Polyethylene (PE), polypropylene (PP), polyvinylidene fluoride (PVDF), Polyimide (PI) and glass fiber paper; the lithium ion battery is a button type lithium ion battery or a soft package lithium ion battery.
Compared with the prior art, the invention has the following beneficial effects:
1) the copper-based sulfide has the advantages of high specific capacity, low price, simple and convenient preparation method and the like, and is beneficial to large-scale production and use. In addition, the copper-based sulfide has good electronic conductivity, and the material can realize the rapid replacement reaction of Cu ions and Li ions in the charge and discharge process by combining the rapid mobility of the Cu ions, so that the material has very rapid charge and discharge kinetic characteristics. Meanwhile, the material has higher working voltage and no risk of lithium precipitation during low-temperature charging and discharging.
2) The copper-based sulfide can be charged and discharged at constant current under the low temperature condition of-60 ℃, and provides specific capacity of 182mAh/g, which is equivalent to 52% of capacity at 25 ℃.
3) The copper-based sulfide has higher working voltage (1.8V relative to Li)+Li), no risk of lithium precipitation during low-temperature charging and discharging, and the constant-current charging and discharging cycle life at-60 ℃ is more than 60 times, thereby providing guarantee for safe and stable charging and discharging of the lithium ion battery under the extreme low-temperature condition.
Drawings
FIG. 1 is a drawing showing cuprous sulfide Cu in example 1 of the present invention2An X-ray diffraction pattern of the S material;
FIG. 2 is a drawing showing cuprous sulfide Cu in example 1 of the present invention2S material in Cu2In the S | | lithium metal battery, under the current density of 100mA/g, charge-discharge voltage-specific capacity curve diagrams at 25 ℃, 20 ℃, 40 ℃ and 60 ℃ respectively;
FIG. 3 is a drawing showing cuprous sulfide Cu in example 1 of the present invention2S material in Cu2In an S | lithium metal battery, a circulation stability chart at-60 ℃ under the current density of 100 mA/g;
FIG. 4 shows Cu in example 2 of the present invention2The charging and discharging voltage-specific capacity curve diagrams of the S | | | NCM811 lithium ion battery at 25 ℃ and-40 ℃ respectively under the current density of 15 mA/g.
Detailed Description
The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application, and it is obvious that the described embodiments are only examples and are not intended to limit the present application.
The invention comprises a battery cathode material, an anode material, electrolyte and a diaphragm; the cathode material of the low-temperature battery is copper-based sulfide CuxS (x is more than or equal to 1 and less than or equal to 2), and the anode material is a nickel-cobalt-manganese (NCM) ternary material, a nickel-cobalt-aluminum (NCA) ternary material or lithium iron phosphate (LiFePO)4) Material, lithium cobaltate (LiCoO)2) Material, lithium manganate (LiMn)2O4) The electrolyte comprises lithium salt and solvent, and the diaphragm separates the positive electrode and the negative electrode and prevents the positive electrode and the negative electrode from being in direct contact with each other to cause short circuit.
In specific implementation, the positive active material in the positive electrode plate is selected from nickel-cobalt-manganese (NCM) ternary material, nickel-cobalt-aluminum (NCA) ternary material, and lithium iron phosphate (LiFePO)4) Material, lithium cobaltate (LiCoO)2) Material, lithium manganate (LiMn)2O4) One of the materials accounts for 70-95 wt%, and the total proportion of the conductive agent and the binder in the positive pole piece is 30-5 wt%. The sum of the mass ratios of the conductive agent, the binder and the positive active material is ensured to be 1. The loading amount of the positive active material can be controlled to be 2mg/cm2～10mg/cm2And (3) a range.
In specific implementation, the negative active material in the negative pole piece is copper-based sulfide CuxS (x is more than or equal to 1 and less than or equal to 2), the proportion of the S is 70-95 wt%, and the total proportion of the conductive agent and the binder in the negative pole piece is 30-5 wt%. The sum of the mass ratios of the conductive agent, the binder and the negative active material is ensured to be 1. The loading amount of the negative active material can be controlled to be 1mg/cm2～5mg/cm2And (3) a range.
In specific implementation, in the lithium ion battery provided by the invention, the capacity ratio of the negative electrode plate to the positive electrode plate can be controlled within the range of 1.1: 1-1.2: 1.
In specific implementation, the conductive agent used in the positive electrode plate and the negative electrode plate may be one or more of acetylene black, ketjen black, carbon nanotubes, and graphene. The positive electrode plate and the negative electrode plate may use the same conductive agent, or the positive electrode plate and the negative electrode plate may also use two different conductive agents, which is not limited herein.
In specific implementation, the binder used in the positive electrode plate is one of polyvinylidene fluoride (PVDF) and Polytetrafluoroethylene (PTFE), and the current collector is an aluminum foil.
In specific implementation, the binder used in the negative electrode plate is one of polyvinylidene fluoride (PVDF), Polytetrafluoroethylene (PTFE), polyvinyl alcohol (PVA), sodium carboxymethylcellulose (CMC), and sodium alginate, and the current collector is one of aluminum foil or copper foil.
In specific implementation, the total ratio of the conductive agent to the binder in the positive and negative plates is 30 wt.% to 5 wt.%.
In a specific implementation, the lithium ion battery electrolyte comprises a solvent and a lithium salt, and the electrolyte solvent is selected from one or more of 1, 3-Dioxolane (DOL), ethylene glycol dimethyl ether (DME), diethylene glycol dimethyl ether (DEGDME), triethylene glycol dimethyl ether (TEGDME) and tetraethylene glycol dimethyl ether (Tetraglyme). The lithium salt of the electrolyte is lithium hexafluorophosphate (LiPF)6) Lithium bis (fluorosulfonylimide) (LiFSI), lithium trifluoromethanesulfonate (LiCF)3SO3) Lithium bistrifluoromethanesulfonimide (LiTFSI), lithium perchlorate (LiClO)4) Lithium tetrafluoroborate (LiBF)4) One or more of lithium bis (oxalato) borate (LiBOB) and lithium difluoro (oxalato) borate (LiDFOB) at a concentration of 0.5 to 3 mol/L.
In specific implementation, the lithium ion battery separator may be selected from one of Polyethylene (PE), polypropylene (PP), polyvinylidene fluoride (PVDF), Polyimide (PI), and glass fiber paper.
In specific implementations, the lithium metal is a lithium sheet having a thickness of 30-150 μm.
It should be noted that the lithium ion battery provided by the present invention may be a button type lithium ion battery, or may also be a soft package lithium ion battery, which is not limited herein.
In specific implementation, when the binder used in the battery pole piece is polyvinylidene fluoride (PVDF), the solvent used for preparing the slurry is N-methyl pyrrolidone; when the binder used in the electrode plate is Polytetrafluoroethylene (PTFE), the solvent used for preparing the slurry is isopropanol; when the binder used in the electrode plate is sodium carboxymethylcellulose (CMC), the solvent used for preparing the slurry is water; when the adhesive used in the electrode plate is sodium alginate, the solvent used for preparing the slurry is water.
In the process of preparing the electrode slurry, the solvent is mixed with the active material, the binder and the conductive agent in an undefined ratio, and the mixture is stirred uniformly to form a slurry.
The following will explain the specific implementation process of the present invention in detail by taking the preparation of lithium ion button cell as an example through specific examples.
Example 1
(1) Preparing a negative pole piece: using commercial cuprous sulphide Cu2S as the negative active material, fig. 1 shows the X-ray diffraction spectrum of the negative material, which proves that it is monoclinic cuprous sulfide. Mixing the negative active material, the conductive agent Keqin black and the adhesive sodium alginate according to the mass ratio of 7:2:1, adding water, uniformly stirring, uniformly coating on a copper foil current collector, and drying in vacuum at 80 ℃ to obtain a negative pole piece, wherein the loading capacity of the negative active material is 3mg/cm2。
(2) Preparing a half cell: the method comprises the steps of taking a metal lithium foil as a counter electrode, taking glass fiber as a diaphragm, selecting 1mol/L lithium bis (trifluoromethanesulfonylimide) (LiTFSI) as an electrolyte, dissolving the lithium bis (trifluoromethanesulfonimide) (LiTFSI) in a mixed solution of 1, 3-Dioxolane (DOL) and ethylene glycol dimethyl ether (DME) (DOL: DME: 1 Vol%), assembling a button cell in a glove box with water and oxygen content lower than 0.1ppm according to the sequence of a negative electrode shell, a spring plate, a gasket, a lithium sheet, the electrolyte, the diaphragm, the electrolyte, a negative electrode sheet, the gasket and a positive electrode shell, and compacting the cell by using a button cell sealing machine after assembly to perform subsequent tests. And standing for 4 hours after the battery is assembled, performing constant current charge and discharge test at 25 ℃ by using a blue battery test system, circulating for 5-10 circles, and performing charge and discharge test in a constant temperature box at-20 ℃, 40 ℃ and 60 ℃. FIG. 2 shows the charge-discharge voltage-specific capacity curves at 25 deg.C, -20 deg.C, -40 deg.C and-60 deg.C of the battery, even at-60 deg.C the battery can maintain the specific capacity of 182mAh/g under the constant current charge-discharge of 100mA/g, and the capacity retention rate is equivalent to 52% of the capacity at 25 deg.C. FIG. 3 shows that the battery has a charge-discharge specific capacity of 80 cycles at-60 ℃, and after 60 cycles, the charge-discharge specific capacity is kept at 185mAh/g, and the cycle performance is excellent.
Example 2
(1) Preparing a negative pole piece: the negative electrode sheet was prepared by the method of step (1) of example 1.
(2) Preparing a positive pole piece: using commercial NMC811 as a positive active substance, mixing a positive active material, a conductive agent Keqin black and a binder PVDF according to a mass ratio of 7:2:1, adding N-methyl pyrrolidone, uniformly stirring, uniformly coating on an aluminum foil current collector, and drying in vacuum at 80 ℃ to obtain a positive pole piece, wherein the loading capacity of the positive active material is 7mg/cm2。
(3) Preparing a lithium ion battery: the method comprises the steps of taking glass fiber as a diaphragm, dissolving 1mol/L lithium bistrifluoromethanesulfonylimide (LiTFSI) in a mixed solution of 1, 3-Dioxolane (DOL) and ethylene glycol dimethyl ether (DME) (DOL: DME: 1 Vol%), assembling a button cell in a glove box with water and oxygen content lower than 0.1ppm according to the sequence of a negative electrode shell, a spring plate, a gasket, a negative electrode piece, electrolyte, the diaphragm, the electrolyte, a positive electrode piece, the gasket and a positive electrode shell, and compacting the cell by using a button cell sealing machine after assembling to perform subsequent tests. And standing for 4 hours after the battery is assembled, performing constant current charge and discharge test at 25 ℃ by using a blue battery test system, circulating for 5-10 circles, and performing constant current charge and discharge test in a constant temperature box at-20 ℃, 40 ℃ and 60 ℃. FIG. 4 shows the charge-discharge voltage-specific capacity curves of the battery at 25 ℃ and-40 ℃ respectively, and the battery can still maintain the charge-discharge specific capacity of 70mAh/g at-40 ℃, and the capacity retention rate is equal to 43.75% of the capacity at 25 ℃.
Although the methods and techniques of the present invention have been described in terms of preferred embodiments, it will be apparent to those of ordinary skill in the art that variations and/or rearrangements of the methods and techniques described herein may be made without departing from the spirit and scope of the invention. It is expressly intended that all such similar substitutes and modifications apparent to those skilled in the art are deemed to be within the spirit, scope and content of the invention.
Claims (10)
1. The negative electrode material of the low-temperature charge-discharge lithium ion battery is characterized by comprising a negative electrode active material, a conductive agent and a binder, wherein the negative electrode active material is a copper-based sulfide CuxS, x is more than or equal to 1 and less than or equal to 2, and CuxThe mass ratio of S is 70-95 wt.%, and the total mass ratio of the conductive agent and the adhesive is 30-5 wt.%; the sum of the mass ratios of the negative electrode active material, the conductive agent and the binder is 1; the loading amount of the negative active material is 1mg/cm2～5mg/cm2。
2. A low-temperature charge-discharge lithium ion battery is characterized by comprising a negative pole piece, a positive pole piece, electrolyte and a diaphragm; the negative active material of the negative pole piece is copper-based sulfide CuxS, 1 is more than or equal to x is less than or equal to 2, and the positive active material of the positive pole piece is a nickel-cobalt-manganese (NCM) ternary material, a nickel-cobalt-aluminum (NCA) ternary material and lithium iron phosphate (LiFePO)4) Material, lithium cobaltate (LiCoO)2) Material, lithium manganate (LiMn)2O4) In one material, the electrolyte comprises lithium salt and solvent, and the positive pole piece and the negative pole piece are separated by a diaphragm.
3. The low temperature charge-discharge lithium ion battery of claim 2, which isCharacterized in that the CuxThe mass ratio of S is 70-95 wt.%; the negative pole piece further comprises a conductive agent and a binder, wherein the total mass ratio of the conductive agent to the binder is 30-5 wt.%; the loading amount of the negative active material is 1mg/cm2～5mg/cm2。
4. The low-temperature charge-discharge lithium ion battery according to claim 3, wherein the binder of the negative electrode plate is one of polyvinylidene fluoride (PVDF), Polytetrafluoroethylene (PTFE), polyvinyl alcohol (PVA), sodium carboxymethylcellulose (CMC) and sodium alginate, and the current collector of the negative electrode plate is one of aluminum foil or copper foil.
5. The low-temperature charge-discharge lithium ion battery according to any one of claims 2 to 4, wherein the mass ratio of the positive electrode active material is 70 wt.% to 95 wt.%; the positive pole piece further comprises a conductive agent and a binder, the mass ratio of the conductive agent to the binder is 30-5 wt.%, and the sum of the mass ratios of the positive active material, the conductive agent and the binder is 1; the loading amount of the positive active material is 2mg/cm2～10mg/cm2。
6. The low-temperature charge-discharge lithium ion battery according to claim 5, wherein the binder of the positive electrode plate is one of polyvinylidene fluoride (PVDF) and Polytetrafluoroethylene (PTFE), and the current collector of the positive electrode plate is an aluminum foil.
7. The low-temperature charge-discharge lithium ion battery according to claim 5, wherein the conductive agent of the positive electrode plate and the negative electrode plate is one or more of acetylene black, Ketjen black, carbon nanotubes and graphene.
8. The low-temperature charge-discharge lithium ion battery as claimed in claim 2, wherein the capacity ratio of the negative electrode plate to the positive electrode plate is 1.1: 1-1.2: 1.
9. The low-temperature charge-discharge lithium ion battery according to claim 2, wherein the electrolyte solvent is one or more of 1, 3-Dioxolane (DOL), ethylene glycol dimethyl ether (DME), diethylene glycol dimethyl ether (DEGDME), triethylene glycol dimethyl ether (TEGDME), and tetraethylene glycol dimethyl ether (Tetraglyme), and the lithium salt of the electrolyte is lithium hexafluorophosphate (LiPF)6) Lithium bis (fluorosulfonylimide) (LiFSI), lithium trifluoromethanesulfonate (LiCF)3SO3) Lithium bistrifluoromethanesulfonimide (LiTFSI), lithium perchlorate (LiClO)4) Lithium tetrafluoroborate (LiBF)4) One or more of lithium bis (oxalato) borate (LiBOB) and lithium difluoro (oxalato) borate (LiDFOB), wherein the concentration of the lithium salt is 0.5-3 mol/L.
10. The low-temperature charge-discharge lithium ion battery according to claim 2, wherein the separator is one of Polyethylene (PE), polypropylene (PP), polyvinylidene fluoride (PVDF), Polyimide (PI) and glass fiber paper; the lithium ion battery is a button type lithium ion battery or a soft package lithium ion battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210151180.8A CN114400321A (en) | 2022-02-15 | 2022-02-15 | Low-temperature charge-discharge lithium ion battery and negative electrode material thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210151180.8A CN114400321A (en) | 2022-02-15 | 2022-02-15 | Low-temperature charge-discharge lithium ion battery and negative electrode material thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114400321A true CN114400321A (en) | 2022-04-26 |
Family
ID=81234133
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210151180.8A Pending CN114400321A (en) | 2022-02-15 | 2022-02-15 | Low-temperature charge-discharge lithium ion battery and negative electrode material thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114400321A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114975994A (en) * | 2022-06-17 | 2022-08-30 | 北京航空航天大学 | Low-temperature quick-charging lithium ion battery cathode material and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103219491A (en) * | 2013-03-29 | 2013-07-24 | 湘潭大学 | Copper sulfide anode and preparation method thereof |
| US20170125794A1 (en) * | 2014-04-21 | 2017-05-04 | Xiamen University | A sulfur-based transition metal composite and the negative electrode comprising the same and the battery comprising the same |
| CN106887337A (en) * | 2012-06-01 | 2017-06-23 | 株式会社半导体能源研究所 | Electrical storage device negative pole and electrical storage device |
| CN113937336A (en) * | 2021-09-20 | 2022-01-14 | 复旦大学 | Wide-temperature mixed ion battery based on lithium iron phosphate anode and tin-carbon cathode |
-
2022
- 2022-02-15 CN CN202210151180.8A patent/CN114400321A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106887337A (en) * | 2012-06-01 | 2017-06-23 | 株式会社半导体能源研究所 | Electrical storage device negative pole and electrical storage device |
| CN103219491A (en) * | 2013-03-29 | 2013-07-24 | 湘潭大学 | Copper sulfide anode and preparation method thereof |
| US20170125794A1 (en) * | 2014-04-21 | 2017-05-04 | Xiamen University | A sulfur-based transition metal composite and the negative electrode comprising the same and the battery comprising the same |
| CN113937336A (en) * | 2021-09-20 | 2022-01-14 | 复旦大学 | Wide-temperature mixed ion battery based on lithium iron phosphate anode and tin-carbon cathode |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114975994A (en) * | 2022-06-17 | 2022-08-30 | 北京航空航天大学 | Low-temperature quick-charging lithium ion battery cathode material and preparation method and application thereof |
| CN114975994B (en) * | 2022-06-17 | 2024-02-13 | 北京航空航天大学 | Low-temperature quick-chargeable lithium ion battery anode material and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108539182B (en) | Preparation method of composite sulfur positive electrode material and application of composite sulfur positive electrode material in all-solid-state lithium-sulfur battery | |
| CN110752408B (en) | Electrolyte, preparation method thereof and lithium ion battery | |
| CN110416597B (en) | Ether electrolyte and lithium-sulfur secondary battery | |
| CN113097448A (en) | Lithium-supplementing negative electrode and application thereof | |
| CN114447333B (en) | Sodium ion battery | |
| CN111834620A (en) | Lithium metal battery positive electrode, lithium metal battery and preparation method thereof | |
| WO2022262230A1 (en) | Non-aqueous electrolyte and secondary battery thereof | |
| CN111952670A (en) | Lithium ion battery with wide working temperature range | |
| CN111525190A (en) | Electrolyte and lithium ion battery | |
| CN109962231B (en) | Metal foil used as lanthanum ion secondary battery cathode, lanthanum ion secondary battery and preparation method thereof | |
| WO2019095717A1 (en) | Lithium primary cell | |
| CN114400321A (en) | Low-temperature charge-discharge lithium ion battery and negative electrode material thereof | |
| CN107565097A (en) | Double collector sulphur positive poles and preparation method thereof and the application in lithium-sulfur cell | |
| CN114614096B (en) | Quick-charging electrolyte and application thereof in lithium ion battery | |
| CN115207335A (en) | Low-temperature chargeable and dischargeable lithium ion battery cathode material and lithium ion battery | |
| CN114156541A (en) | Electrolyte additive, electrolyte containing additive and lithium ion battery | |
| CN115995598A (en) | Multifunctional sodium battery electrolyte additive and application thereof | |
| CN113964454A (en) | High-energy-density non-negative lithium battery | |
| CN111129575A (en) | Special battery for new energy equipment | |
| CN112803072A (en) | Lithium battery electrolyte and lithium battery | |
| CN113764728A (en) | Electrolyte and lithium metal battery | |
| CN104157908A (en) | Lithium salt electrolyte, preparation method and application thereof | |
| CN115954550B (en) | All-weather lithium ion battery electrolyte, battery and charging and discharging method | |
| CN115472914B (en) | Electrolyte of lithium-sulfur battery with high sulfur surface loading and lithium-sulfur battery with high sulfur surface loading | |
| CN113659200B (en) | Electrolyte additive for improving high-temperature performance of lithium battery, electrolyte and electrochemical device |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |