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CN111952670A - Lithium ion battery with wide working temperature range - Google Patents

Lithium ion battery with wide working temperature range Download PDF

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Publication number
CN111952670A
CN111952670A CN202010666064.0A CN202010666064A CN111952670A CN 111952670 A CN111952670 A CN 111952670A CN 202010666064 A CN202010666064 A CN 202010666064A CN 111952670 A CN111952670 A CN 111952670A
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lithium
ion battery
lithium ion
electrolyte
temperature range
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王永刚
鄢蕾
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Fudan University
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Fudan University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0569—Liquid materials characterised by the solvents
    • 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
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • H01M2300/0028—Organic electrolyte characterised by the solvent
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
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  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Secondary Cells (AREA)

Abstract

The invention belongs to the technical field of electrochemistry, and particularly relates to a lithium ion battery with a wide working temperature range. The lithium ion battery consists of a positive electrode, a negative electrode and electrolyte; wherein the positive electrode material is an intercalation compound; the negative electrode is one or a mixture of more of an intercalation compound, an oxide, a sulfide, elemental sulfur and a porous carbon material; the electrolyte takes N, N-dimethylformamide as a main solvent, takes organic lithium salt and/or inorganic lithium salt as a solute, has the characteristics of high boiling point and low freezing point, and is in a wider temperature range (-60)oThe ionic conductivity is good at C-150 ℃. Different from the traditional lithium ion battery, the lithium ion battery provided by the invention can be in the range of-60 DEGoThe high-temperature-resistant energy storage device can stably work within the temperature range of C-150 ℃, shows good cycle performance and power characteristics, and can be used as an energy storage device in areas with high cold, high temperature and large environmental temperature change.

Description

Lithium ion battery with wide working temperature range
Technical Field
The invention belongs to the technical field of batteries, and particularly relates to a lithium ion battery with a wide working temperature range.
Background
As a highly efficient electrochemical energy conversion and storage device, secondary batteries have become an essential item for human life. Among them, lithium ion batteries having high energy density, long cycle life and no memory effect occupy the major battery market, and are widely used in 3C products such as mobile phones, notebook computers, digital cameras, etc., and are being used as power systems of electric vehicles. In addition, the lithium ion battery has wide application prospect in the field of large-scale energy storage.
However, it is well known that lithium ion batteries can normally operate only in the temperature range of-40 ℃ to 60 ℃, which greatly limits their use in ultra-low temperature, ultra-high temperature, or regions with large temperature variation ranges. As described in the literature, the conventional lithium ion battery discharge capacity is only 20% of the room temperature capacity at-40 ℃. The main reasons are as follows: temperatures below-40 ℃ approach or reach the freezing point of the electrolyte, where the electrolyte exhibits very low ionic conductance and very high viscosity (or has solidified), thus greatly increasing the interfacial resistance of the electrode reaction. On the other hand, under high temperature conditions, the electrolyte is easily decomposed by oxidation, which results in an increase in the resistance of the SEI film on the surface of the electrode, and even destroys the internal structure of the bulk material of the electrode, causing the risk of explosion. Therefore, conventional lithium ion batteries may note that: it must be used at temperatures below 60 ℃.
As described above, the development of an electrolyte having a high boiling point, a low freezing point, and a high ionic conductivity over a wide temperature range is an important means for improving the high and low temperature performance of a lithium ion battery. However, very few electrolytes can meet both high and low boiling point requirements. The invention provides a lithium ion electrolyte with a wide working temperature range, which takes N, N-dimethylformamide as a main solvent. N, N-dimethylformamide is a polar aprotic solvent, contains carbonyl and amino polar groups, and can effectively dissolve organic or inorganic lithium salts. In addition, the N, N-dimethylformamide has the advantages of high boiling point, low freezing point, small viscosity, high dielectric constant, good redox stability, low price and the like. However, it is noteworthy that: the stable potential window of N, N-dimethylformamide solvent is limited, which is below 1V (vs. Li/Li)+) Decomposition occurs at this time, and thus cannot be applied to a conventional lithium ion battery. The invention firstly combines the lead-free tin oxide with high working potential (more than 1V vs. Li/Li)+) The cathode is combined to construct a lithium ion battery system which can stably work in an ultra-wide temperature range (minus 60 ℃ to 150 ℃).
Disclosure of Invention
The invention aims to provide a lithium ion battery which has low cost, long cycle life, high energy density, excellent high and low temperature performance and wide working temperature range.
The lithium ion battery with wide working temperature range provided by the invention comprises a positive electrode, a negative electrode and electrolyte; wherein the positive electrode active material is an intercalation compound; the negative active material is one or a mixture of more of an intercalation compound, an oxide, a sulfide, elemental sulfur and a porous carbon material; the electrolyte is a wide temperature range electrolyte, specifically N, N-dimethylformamide is used as a main solvent, organic lithium salt and/or inorganic lithium salt is used as a solute, and a certain amount of auxiliary solvent, film forming additive and flame retardant additive can be contained; the electrolyte shows high ionic conductance in a wide temperature range (-60 ℃ -150 ℃).
The working principle of the battery is that Li is mainly used in the process of charging and discharging+Embedding and releasing between the positive electrode and the negative electrode back and forth: upon charging, Li+The lithium ion battery is taken out from the positive electrode and is inserted into the negative electrode through the electrolyte, and the negative electrode is in a lithium-rich state; the opposite is true during discharge.
In the invention, the main solvent of the wide temperature range electrolyte is N, N-dimethylformamide, and an auxiliary solvent can be added, wherein the auxiliary solvent is one or more selected from N, N-dimethylacetamide, water, ethylene carbonate, propylene carbonate, dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, ethyl acetate and dimethyl sulfoxide. The auxiliary solvent is mainly used for adjusting the viscosity and the corresponding ionic conductivity of the electrolyte at high temperature or low temperature.
In the electrolyte with a wide temperature range, the solute is selected from organic lithium salts and inorganic lithium salts, and specifically, is selected from one or more of lithium trifluoromethanesulfonate, lithium bis (trifluoromethanesulfonylimide), lithium tris (trifluoromethanesulfonylmethyl) lithium, lithium bis (fluorosulfonyl) imide, lithium perchlorate, lithium tetrafluoroborate, lithium hexafluorophosphate, lithium sulfate, lithium nitrate, lithium carbonate, lithium oxalate, lithium formate and lithium acetate.
In the invention, the concentration range of lithium ions contained in the electrolyte with the wide temperature range is 0.1-10 mol/L.
In the electrolyte with the wide temperature range, the electrolyte film-forming additive is selected from one or more of borate, sulfite, sultone, fluoroethylene ester and polyoxyethylene ether. The additive mainly functions to facilitate the formation of a uniform SEI film, thereby reducing interfacial resistance.
In the electrolyte with the wide temperature range, the electrolyte flame retardant additive is selected from one or more of trimethyl phosphate, triethyl phosphate, tributyl phosphate, triphenyl phosphate, isopropylbenzenediphenyl phosphate, tolyldiphenyl phosphate, hexamethoxyphosphazene, tris (2, 2, 2-trifluoroethyl) phosphate, bis (2, 2, 2-trifluoroethyl) methylphosphonic acid, bis (2, 2, 2-trifluoroethyl) diethyl ester and hexamethylphosphoramide.
In the invention, the positive electrode and the negative electrode are respectively composed of an active material, a conductive agent, a binder and a current collector.
In the present invention, the active material of the positive electrode is an intercalation compound selected from lithium manganate (LiMn)2O4) Lithium-rich lithium manganate (Li)1+xMn2O4(x is 0-0.1) and lithium manganate (LiM) doped with transition metal element MxMn2-xO4M is one or more of Al, Mg, Zn and Co, (x is 0-0.05)), and lithium cobaltate (LiCoO)2) Ternary material (LiNi)xCoyMnzO2,0<x、y、z<1) Lithium nickel cobalt aluminum material (LiNi)0.80Co0.15Al0.05O2) Lithium iron phosphate (LiFePO)4) Lithium manganese phosphate (LiMnPO)4) Manganese iron phosphate (LiMn)1-xFexPO4And (x ═ 0.05 to 0.2)) in a solvent.
In the present invention, the active material of the negative electrode is selected from lithium titanium phosphate (LiTi)2(PO4)3)、Sodium titanium phosphate (NaTi)2(PO4)3) Titanium pyrophosphate (TiP)2O7) Lithium titanate (Li)4Ti5O12) Iron phosphate (FePO)4) Lithium iron silicate (Li)2FeSiO4) Titanium dioxide (TiO)2) Iron oxide (Fe)2O3,Fe3O4) One or more of elemental sulfur (S), carbon-sulfur compounds, activated carbon, carbon nanotubes, mesoporous carbon, graphene and carbon fibers.
In the positive and negative electrodes, the current collector is one or a compound of a plurality of titanium meshes, titanium foils, stainless steel meshes, porous stainless steel bands, stainless steel foils, aluminum meshes, carbon cloth, carbon meshes, carbon felts, copper meshes and copper foils.
In the positive electrode and the negative electrode, the binder is one or more of Polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), carboxymethyl cellulose (CMC), water-soluble rubber and polyvinyl alcohol (PVA).
In the positive electrode and the negative electrode, the conductive additive is one or more of activated carbon, acetylene black, carbon nano tubes, carbon fibers, graphene, graphite and mesoporous carbon.
Different from the traditional lithium ion battery, the lithium ion battery provided by the invention can stably work in the temperature range of-60-150 ℃, shows good cycle performance and power characteristics, and can be used as an energy storage device in areas with high cold, high temperature and large environmental temperature change.
Detailed Description
To further clearly illustrate the technical solutions and advantages of the present invention, the present invention is described by the following specific examples, but the present invention is not limited to these examples.
Example 1
The wide temperature electrolyte is obtained by dissolving lithium nitrate in N, N-dimethylformamide at concentrations of 1, 5 and 10mol/L with N, N-dimethylformamide as a solvent. With lithium manganate (LiMn)2O4) As a positive electrode active material. The preparation of the positive electrode plate is as follows: according to the active material (LiMn)2O4): conductive agent (acetylene)Black): and (3) mixing the slurry with a binder (polytetrafluoroethylene PTFE) in a ratio of 80:10:10, rolling to form a membrane, drying, cutting, and pressing on a titanium mesh to form the positive electrode plate. In this example, the coating amount of the positive electrode was 5mg cm-2. Secondly, lithium titanium phosphate (LiTi)2(PO4)3) Is a negative electrode active material. The preparation of the negative electrode slice is as follows: according to the active material (LiTi)2(PO4)3): conductive agent (acetylene black): and (3) mixing the slurry with a binder (polytetrafluoroethylene PTFE) in a ratio of 80:10:10, rolling to form a membrane, drying, cutting, and pressing on a titanium mesh to form the negative electrode plate. In this example, the coating amount of the negative electrode was 6.5mg cm-2. And then, assembling the lithium ion button cell by taking glass fiber as a cell diaphragm. The assembled lithium ion battery is subjected to charge and discharge tests on an electrochemical workstation at a multiplying power of 0.1C, and the specific capacity is 100mAh g at the normal temperature of 25 DEG C-1(calculated based on the mass of the positive active material), the specific capacity is 60mAh g at the low temperature of-60 DEG C-1The capacity reaches 102mAh g at the high temperature of 150 DEG C-1(see Table 1). And after 10000 cycles of circulation at the current density of 0.5C at the normal temperature of 25 ℃, the capacity retention rate reaches 90 percent (see table 2).
Example 2
Dissolving lithium nitrate in N, N-dimethylformamide according to the concentration of 1, 5 and 10mol/L by taking N, N-dimethylformamide as a solvent, and adding 5% trimethyl phosphate as a flame retardant to obtain the wide-temperature electrolyte. With lithium manganate (LiMn)2O4) As a positive electrode active material. The preparation of the positive electrode plate is as follows: according to the active material (LiMn)2O4): conductive agent (acetylene black): and (3) mixing the slurry with an adhesive (polytetrafluoroethylene PTFE) in a ratio of 80:10:10, rolling to form a film, drying, cutting, and pressing on a titanium mesh to obtain the positive pole piece. In this example, the coating amount of the positive electrode was 5mg cm-2. Secondly, lithium titanium phosphate (LiTi)2(PO4)3) Is a negative electrode active material. The preparation of the negative electrode slice is as follows: according to the active material (LiTi)2(PO4)3): conductive agent (acetylene black): mixing the slurry with the binder (polytetrafluoroethylene PTFE) in a ratio of 80:10:10, rolling to form a filmDrying, cutting and pressing on a titanium mesh to form the negative electrode plate. In this example, the coating amount of the negative electrode was 6.5mg cm-2. And then, assembling the lithium ion button cell by taking glass fiber as a cell diaphragm. The assembled lithium ion battery is subjected to charge and discharge tests on an electrochemical workstation at a multiplying power of 0.1C, and the specific capacity of the assembled lithium ion battery is 98mAh g at the normal temperature of 25 DEG C-1(calculated based on the mass of the positive active material), the specific capacity is 56mAh g at the low temperature of-60 DEG C-1The capacity reaches 100mAh g at high temperature of 150 DEG C-1(see Table 1). And after 10000 cycles of circulation at the current density of 0.5C at the normal temperature of 25 ℃, the capacity retention rate reaches 92 percent (see table 2).
Example 3
The wide temperature electrolyte is obtained by dissolving lithium nitrate in N, N-dimethylformamide at concentrations of 1, 5 and 10mol/L with N, N-dimethylformamide as a solvent. With lithium manganate (LiMn)2O4) As a positive electrode active material. The preparation of the positive electrode plate is as follows: according to the active material (LiMn)2O4): conductive agent (acetylene black): and (3) mixing the slurry with an adhesive (polytetrafluoroethylene PTFE) in a ratio of 80:10:10, rolling to form a film, drying, cutting, and pressing on a titanium mesh to obtain the positive pole piece. In this example, the coating amount of the positive electrode was 5mg cm-2. Secondly, lithium titanium phosphate (LiTi)2(PO4)3) The compound with 10 wt% of active carbon is a negative active material. The preparation of the negative electrode slice is as follows: according to the active material (LiTi)2(PO4)3+10 wt% AC): conductive agent (acetylene black): and (3) mixing the slurry with a binder (polytetrafluoroethylene PTFE) in a ratio of 80:10:10, rolling to form a membrane, drying, cutting, and pressing on a titanium mesh to form the negative electrode plate. In this example, the coating amount of the negative electrode was 6.5mg cm-2. And then, assembling the lithium ion button cell by taking glass fiber as a cell diaphragm. The assembled lithium ion battery is subjected to charge and discharge tests on an electrochemical workstation at a multiplying power of 0.1C, and the specific capacity of the assembled lithium ion battery is 103mAh g at the normal temperature of 25 DEG C-1(calculated based on the mass of the positive active material), the specific capacity is 62mAh g at the low temperature of-60 DEG C-1The capacity reaches 104mAh g at the high temperature of 150 DEG C-1. (see Table 1). And at normal temperature of 25 DEG CAfter 10000 cycles of circulation at a current density of 0.5C, the capacity retention rate reaches 95% (see Table 2).
Example 4
The wide temperature electrolyte is obtained by dissolving lithium nitrate in N, N-dimethylformamide at concentrations of 1, 5 and 10mol/L with N, N-dimethylformamide as a solvent. With lithium manganate (LiMn)2O4) As a positive electrode active material. The preparation of the positive electrode plate is as follows: according to the active material (LiMn)2O4): conductive agent (acetylene black): and (3) mixing the slurry with an adhesive (polytetrafluoroethylene PTFE) in a ratio of 80:10:10, rolling to form a film, drying, cutting, and pressing on a titanium mesh to obtain the positive pole piece. In this example, the coating amount of the positive electrode was 5mg cm-2. Secondly, sodium titanium phosphate (NaTi)2(PO4)3) Is a negative electrode active material. The preparation of the negative electrode slice is as follows: according to the active material (NaTi)2(PO4)3): conductive agent (acetylene black): and (3) mixing the slurry with a binder (polytetrafluoroethylene PTFE) in a ratio of 80:10:10, rolling to form a membrane, drying, cutting, and pressing on a titanium mesh to form the negative electrode plate. In this example, the coating amount of the negative electrode was 5.5mg cm-2. And then, assembling the lithium ion button cell by taking glass fiber as a cell diaphragm. The assembled lithium ion battery is subjected to charge and discharge tests on an electrochemical workstation at a multiplying power of 0.1C, and the specific capacity of the assembled lithium ion battery is 102mAh g at the normal temperature of 25 DEG C-1(calculated based on the mass of the positive electrode active material), the specific capacity is 57mAh g at the low temperature of-60 DEG C-1The capacity reaches 103mAh g at high temperature of 150 DEG C-1. (see Table 1). And after 10000 cycles of circulation at the current density of 0.5C at the normal temperature of 25 ℃, the capacity retention rate reaches 93 percent (see table 2).
Example 5
The wide temperature electrolyte is obtained by dissolving lithium nitrate in N, N-dimethylformamide at concentrations of 1, 5 and 10mol/L with N, N-dimethylformamide as a solvent. With lithium manganate (LiMn)2O4) As a positive electrode active material. The preparation of the positive electrode plate is as follows: according to the active material (LiMn)2O4): conductive agent (acetylene black): mixing the slurry with the binder (polytetrafluoroethylene PTFE) in a ratio of 80:10:10, and rollingAnd drying after preparing a film, cutting, and pressing on a titanium mesh to prepare the positive pole piece. In this example, the coating amount of the positive electrode was 5mg cm-2. Secondly, active carbon is used as a negative electrode active material. The preparation of the negative electrode slice is as follows: according to active substance (activated carbon): conductive agent (acetylene black): and (3) mixing the slurry with a binder (polytetrafluoroethylene PTFE) in a ratio of 80:10:10, rolling to form a membrane, drying, cutting, and pressing on a titanium mesh to form the negative electrode plate. In this example, the coating amount of the negative electrode was 12.5mg cm-2. And then, assembling the lithium ion button cell by taking glass fiber as a cell diaphragm. The assembled lithium ion battery is subjected to charge and discharge tests on an electrochemical workstation at a multiplying power of 0.1C, and the specific capacity of the assembled lithium ion battery is 90mAh g at the normal temperature of 25 DEG C-1(calculated based on the mass of the positive active material), the specific capacity is 50mAh g at the low temperature of-60 DEG C-1The capacity reaches 96mAh g at the high temperature of 150 DEG C-1. (see Table 1). And after 20000 cycles of circulation at 25 ℃ and a current density of 0.5 ℃, the capacity retention rate reaches 95% (see table 2).
Example 6
The wide temperature electrolyte is obtained by dissolving lithium nitrate in N, N-dimethylformamide at concentrations of 1, 5 and 10mol/L with N, N-dimethylformamide as a solvent. With ternary materials (LiNi)0.5Mn1.5O4) As a positive electrode active material. The preparation of the positive electrode plate is as follows: according to the active material (LiNi)0.5Mn1.5O4): conductive agent (acetylene black): and (3) mixing the slurry with an adhesive (polytetrafluoroethylene PTFE) in a ratio of 80:10:10, rolling to form a film, drying, cutting, and pressing on a titanium mesh to obtain the positive pole piece. In this example, the coating amount of the positive electrode was 5mg cm-2. Secondly, lithium titanium phosphate (LiTi)2(PO4)3) Is a negative electrode active material. The preparation of the negative electrode slice is as follows: according to the active material (LiTi)2(PO4)3): conductive agent (acetylene black): and (3) mixing the slurry with a binder (polytetrafluoroethylene PTFE) in a ratio of 80:10:10, rolling to form a membrane, drying, cutting, and pressing on a titanium mesh to form the negative electrode plate. In this example, the coating amount of the negative electrode was 9mg cm-2. Then, the glass fiber is used as a battery diaphragm,and assembling the lithium ion button cell. The assembled lithium ion battery is subjected to charge and discharge tests on an electrochemical workstation at a multiplying power of 0.1C, and the specific capacity is 125mAh g at the normal temperature of 25 DEG C-1(calculated based on the mass of the positive active material), the specific capacity is 88mAh g at the low temperature of-60 DEG C-1The capacity reaches 136mAh g at the high temperature of 150 DEG C-1. (see Table 1). And after 10000 cycles of circulation at the current density of 0.5C at the normal temperature of 25 ℃, the capacity retention rate reaches 88 percent (see table 2).
Example 7
The wide temperature electrolyte is obtained by dissolving lithium sulfate in N, N-dimethylformamide at concentrations of 1, 5 and 10mol/L with N, N-dimethylformamide as a solvent. With lithium manganate (LiMn)2O4) As a positive electrode active material. The preparation of the positive electrode plate is as follows: according to the active material (LiMn)2O4): conductive agent (acetylene black): and (3) mixing the slurry with a binder (polytetrafluoroethylene PTFE) in a ratio of 80:10:10, rolling to form a membrane, drying, cutting, and pressing on a titanium mesh to form the positive electrode plate. In this example, the coating amount of the positive electrode was 5mg cm-2. Secondly, lithium titanium phosphate (LiTi)2(PO4)3) Is a negative electrode active material. The preparation of the negative electrode slice is as follows: according to the active material (LiTi)2(PO4)3): conductive agent (acetylene black): and (3) mixing the slurry with a binder (polytetrafluoroethylene PTFE) in a ratio of 80:10:10, rolling to form a membrane, drying, cutting, and pressing on a titanium mesh to form the negative electrode plate. In this example, the coating amount of the negative electrode was 6mg cm-2. And then, assembling the lithium ion button cell by taking glass fiber as a cell diaphragm. The assembled lithium ion battery is subjected to charge and discharge tests on an electrochemical workstation at a multiplying power of 0.1C, and the specific capacity of the assembled lithium ion battery is 99mAh g at the normal temperature of 25 DEG C-1(calculated based on the mass of the positive electrode active material), the specific capacity is 61mAh g at the low temperature of-60 DEG C-1The capacity reaches 101mAh g at high temperature of 150 DEG C-1. (see Table 1). And after 10000 cycles of circulation at the current density of 0.5C at the normal temperature of 25 ℃, the capacity retention rate reaches 91 percent (see table 2).
Example 8
Under the anhydrous and oxygen-free conditions, using N, N-dimethyl methylAnd (3) dissolving lithium nitrate in N, N-dimethylformamide according to the concentration of 5mol/L by using amide as a solvent to obtain the wide-temperature electrolyte. With lithium manganate (LiMn)2O4) As a positive electrode active material. The preparation of the positive electrode plate is as follows: according to the active material (LiMn)2O4): conductive agent (carbon black): and (3) mixing the adhesive (polyvinylidene fluoride (PVDF)) in a ratio of 80:10:10 to prepare slurry with certain viscosity, forming a film on an aluminum foil, putting the film into a vacuum oven at 80 ℃, and drying for 12 hours to obtain the positive electrode plate. In this example, the coating amount of the positive electrode was 3mg cm-2. Secondly, with lithium titanate (Li)4Ti5O12) Is a negative electrode active material. The preparation of the negative electrode slice is as follows: according to the active substance (Li)4Ti5O12): conductive agent (carbon black): and (3) mixing the binder (carboxymethyl cellulose CMC) in a ratio of 80:10:10 to prepare slurry with certain viscosity, forming a film on a copper foil, putting the copper foil into a vacuum oven at 80 ℃, and drying for 12 hours to obtain the negative electrode plate. In this example, the coating amount of the negative electrode was 2mg cm-2. And then, assembling the lithium ion button cell by taking glass fiber as a cell diaphragm. The assembled lithium ion battery is subjected to charge and discharge tests on an electrochemical workstation at a multiplying power of 0.1C, and the specific capacity of the assembled lithium ion battery is 131mAh g at the normal temperature of 25 DEG C-1(calculated based on the mass of the positive active material), the specific capacity is 96mAh g at the low temperature of-60 DEG C-1The capacity reaches 145mAh g at high temperature of 150 DEG C-1. (see Table 1). And after 5000 cycles at the normal temperature of 25 ℃ and with the current density of 0.5C, the capacity retention rate reaches 85 percent (see table 2).
Example 9
Under the anhydrous and oxygen-free conditions, N-dimethylformamide is used as a solvent, and lithium nitrate is dissolved in the N, N-dimethylformamide according to the concentration of 5mol/L to obtain the wide-temperature electrolyte. With lithium manganate (LiMn)2O4) As a positive electrode active material. The preparation of the positive electrode plate is as follows: according to the active material (LiMn)2O4): conductive agent (carbon black): mixing the binder (polyvinylidene fluoride (PVDF)) at a ratio of 80:10:10 to prepare a slurry with a certain viscosity, forming a film on an aluminum foil, and putting the film into an aluminum foilAnd drying for 12 hours in a vacuum oven at the temperature of 80 ℃ to obtain the positive electrode plate. In this example, the coating amount of the positive electrode was 4mg cm-2. Secondly, with titanium dioxide (TiO)2) Is a negative electrode active material. The preparation of the negative electrode slice is as follows: according to the active substance (TiO)2): conductive agent (carbon black): and (3) mixing the binder (carboxymethyl cellulose CMC) in a ratio of 80:10:10 to prepare slurry with certain viscosity, forming a film on a copper foil, putting the copper foil into a vacuum oven at 80 ℃, and drying for 12 hours to obtain the negative electrode plate. In this example, the coating amount of the negative electrode was 2mg cm-2. And then, assembling the lithium ion button cell by taking glass fiber as a cell diaphragm. The assembled lithium ion battery is subjected to charge and discharge tests on an electrochemical workstation at a multiplying power of 0.1C, and the specific capacity of the assembled lithium ion battery is 165mAh g at the normal temperature of 25 DEG C-1(calculated based on the mass of the negative active material), the specific capacity is 120mAh g at the low temperature of-60 DEG C-1The capacity reaches 170mAh g at high temperature of 150 DEG C-1. (see Table 1). And after 5000 cycles at the normal temperature of 25 ℃ and with the current density of 0.5C, the capacity retention rate reaches 87 percent (see table 2).
Example 10
Under the anhydrous and oxygen-free conditions, N-dimethylformamide is used as a solvent, and bis (trifluoromethylsulfonyl imide) lithium is dissolved in the N, N-dimethylformamide according to the concentration of 1mol/L to obtain the wide-temperature electrolyte. With lithium manganate (LiMn)2O4) As a positive electrode active material. The preparation of the positive electrode plate is as follows: according to the active material (LiMn)2O4): conductive agent (carbon black): and (3) mixing the adhesive (polyvinylidene fluoride (PVDF)) in a ratio of 80:10:10 to prepare slurry with certain viscosity, forming a film on an aluminum foil, putting the film into a vacuum oven at 80 ℃, and drying for 12 hours to obtain the positive electrode plate. In this example, the coating amount of the positive electrode was 3mg cm-2. Secondly, with lithium titanate (Li)4Ti5O12) Is a negative electrode active material. The preparation of the negative electrode slice is as follows: according to the active substance (Li)4Ti5O12): conductive agent (carbon black): the binder (carboxymethyl cellulose CMC) is mixed in a ratio of 80:10:10 to prepare a slurry with a certain viscosity, and then the slurry is formed into a film on a copper foilAnd then putting the anode plate into a vacuum oven at 80 ℃ for drying for 12h to obtain the cathode electrode plate. In this example, the coating amount of the negative electrode was 2mg cm-2. And then, assembling the lithium ion button cell by taking glass fiber as a cell diaphragm. The assembled lithium ion battery is subjected to charge and discharge tests on an electrochemical workstation at a multiplying power of 0.1C, and the specific capacity of the assembled lithium ion battery is 135mAh g at the normal temperature of 25 DEG C-1(calculated based on the mass of the positive electrode active material), the specific capacity is 100mAh g at the low temperature of-60 DEG C-1The capacity reaches 148mAh g at the high temperature of 150 DEG C-1. (see Table 1). And after 5000 cycles at the normal temperature of 25 ℃ and with the current density of 0.5C, the capacity retention rate reaches 89% (see table 2).
TABLE 1 comparison of the Performance of lithium ion batteries using different electrode materials and electrolytes at different temperatures
Figure BDA0002580489900000081
TABLE 2 comparison of the cycle performance of lithium ion batteries using different electrode materials and electrolytes
Figure BDA0002580489900000091

Claims (10)

1. A lithium ion battery with wide working temperature range is characterized by comprising a positive electrode, a negative electrode and electrolyte; wherein the positive electrode active material is an intercalation compound; the negative active material is one or a mixture of more of an intercalation compound, an oxide, a sulfide, elemental sulfur and a porous carbon material; the electrolyte is wide in temperature range, N-dimethylformamide is used as a main solvent, organic lithium salt and/or inorganic lithium salt is used as a solute, and a certain amount of auxiliary solvent, film forming additive and flame retardant additive are also contained; the electrolyte shows high ionic conductance in the temperature range of-60 ℃ to 150 ℃.
2. The lithium ion battery of claim 1, wherein the main solvent of the wide temperature range electrolyte is N, N-dimethylformamide, and an auxiliary solvent is added, wherein the auxiliary solvent is one or more selected from N, N-dimethylacetamide, water, ethylene carbonate, propylene carbonate, dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, ethyl acetate, and dimethylsulfoxide.
3. The lithium ion battery according to claim 1 or 2, wherein in the wide temperature range electrolyte, the solute is selected from one or more of lithium trifluoromethanesulfonate, lithium bis (trifluoromethanesulfonylimide), lithium tris (trifluoromethanesulfonylmethyl), lithium bis (fluorosulfonyl) imide, lithium perchlorate, lithium tetrafluoroborate, lithium hexafluorophosphate, lithium sulfate, lithium nitrate, lithium carbonate, lithium oxalate, lithium formate and lithium acetate.
4. The lithium ion battery of claim 3, wherein the concentration of lithium ions in the electrolyte solution with the wide temperature range is in a range of 0.1-10 mol/L.
5. The lithium ion battery of claim 4, wherein in the electrolyte with the wide temperature range, the electrolyte film forming additive is one or more selected from boric acid esters, sulfurous acid esters, sulfonic acid lactones, fluoroethylene esters and polyoxyethylether.
6. The lithium ion battery of claim 5, wherein in the wide temperature range electrolyte, the electrolyte flame retardant additive is selected from one or more of trimethyl phosphate, triethyl phosphate, tributyl phosphate, triphenyl phosphate, diphenyl isopropenyl phosphate, cresyl diphenyl phosphate, hexamethoxyphosphazene, tris (2, 2, 2 ‒ trifluoroethyl) phosphate, bis (2, 2, 2 ‒ trifluoroethyl) methyl phosphoric acid and (2, 2, 2. trifluoroethyl) diethyl ester, hexamethylphosphoramide.
7. The lithium ion battery of claim 1, whereinCharacterized in that the positive active material is selected from lithium manganate (LiMn)2O4) Lithium-rich lithium manganate (Li)1+xMn2O4) Lithium manganate (LiM) doped with transition metal element MxMn2-xO4M is one or more of Al, Mg, Zn and Co), and lithium cobaltate (LiCoO)2) Ternary material (LiNi)xCoyMnzO2, 0 < x、y、z <1) Lithium nickel cobalt aluminum material (LiNi)0.80Co0.15Al0.05O2) Lithium iron phosphate (LiFePO)4) Lithium manganese phosphate (LiMnPO)4) Manganese iron phosphate (LiMn)1-xFexPO4) One or a mixture of several of them.
8. The lithium ion battery of claim 1, wherein the negative active material is selected from lithium manganate (LiMn)2O4) Lithium-rich lithium manganate (Li)1+xMn2O4(x = 0-0.1) and transition metal element M-doped lithium manganate (LiM)xMn2- xO4M is one or more of Al, Mg, Zn and Co, (x = 0-0.05)), and lithium cobaltate (LiCoO)2) Ternary material (LiNi)xCoyMnzO2, 0 < x、y、z <1) Lithium nickel cobalt aluminum material (LiNi)0.80Co0.15Al0.05O2) Lithium iron phosphate (LiFePO)4) Lithium manganese phosphate (LiMnPO)4) Manganese iron phosphate (LiMn)1-xFexPO4And (x = 0.05-0.2)).
9. The lithium ion battery according to claim 1, wherein the positive electrode and the negative electrode each comprise an active material, a conductive agent, a binder, and a current collector.
10. The lithium ion battery of claim 9, wherein, of the positive and negative electrodes:
the current collector is selected from one or more of a titanium net, a titanium foil, a stainless steel net, a porous stainless steel band, a stainless steel foil, an aluminum net, carbon cloth, a carbon net, a carbon felt, a copper net and a copper foil;
the binder is selected from one or more of polytetrafluoroethylene, polyvinylidene fluoride, carboxymethyl cellulose, water-soluble rubber and polyvinyl alcohol;
the conductive additive is selected from one or more of activated carbon, acetylene black, carbon nanotubes, carbon fibers, graphene, graphite and mesoporous carbon.
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