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CN106356514B - Lithium battery anode, lithium battery and preparation method thereof - Google Patents

Lithium battery anode, lithium battery and preparation method thereof Download PDF

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CN106356514B
CN106356514B CN201610954859.5A CN201610954859A CN106356514B CN 106356514 B CN106356514 B CN 106356514B CN 201610954859 A CN201610954859 A CN 201610954859A CN 106356514 B CN106356514 B CN 106356514B
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lithium
lithium battery
positive electrode
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dimethyl ether
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CN106356514A (en
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赵瑞瑞
李会娜
祝媛
刘建华
刘金成
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Eve Energy Co Ltd
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/362Composites
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/058Construction or manufacture
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/48Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/48Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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    • H01M4/62Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
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    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract

The invention provides a lithium battery anode, a lithium battery anode and a preparation method thereof. Compared with the existing lithium battery, the internal resistance of the lithium battery provided by the invention is remarkably reduced in the working process of the battery, and the battery efficiency is remarkably improved. The production method of the lithium battery provided by the invention has the advantages of simple process flow and simple and convenient operation, and can be used for industrial production of the lithium battery.

Description

Lithium battery anode, lithium battery and preparation method thereof
Technical Field
The invention belongs to the field of batteries, and relates to a lithium battery anode, a lithium battery and a preparation method thereof, in particular to a lithium battery anode containing an anode additive, a lithium battery and a preparation method thereof.
Background
Lithium batteries (Lithium cells) refer to the most basic electrochemical unit of electrochemical Lithium (including metallic Lithium, Lithium alloys and Lithium ions, Lithium polymers). Lithium batteries can be broadly classified into two types: lithium metal batteries and lithium ion batteries. Lithium ion batteries do not contain lithium in the metallic state and are rechargeable. The fifth generation of rechargeable batteries, lithium metal batteries, was born in 1996, and the safety, specific capacity, self-discharge rate and cost performance of rechargeable batteries were all superior to those of lithium ion batteries. Due to its own high technical requirement limits, only a few companies in several countries are currently producing such lithium metal batteries.
Lithium battery anodes, which contain manganese compounds therein, are widely used in the production of lithium batteries due to their beneficial properties. However, in the working process of the lithium battery, the manganese element in the positive electrode is reduced to positive trivalent from positive quadrivalent to electron, the d orbit of the quadrivalent manganese element has three electrons, and t of the three electrons2gTrack dxy、dyzAnd dxzThe manganese is filled with one electron, so that the d-orbital electron distribution of tetravalent manganese is symmetrical, and the octahedral structure of manganese cannot deform; while the d orbital of trivalent manganese has four electrons, egTrack dx2-y2The track is filled with an electron, which results in its egThe orbital electron distribution is asymmetric, thereby causing Jahn-Teller effect, causing the deformation of manganese octahedral structure, and leading to the instability of trivalent manganese in crystal lattice. Due to the instability of trivalent manganese, part of manganese enters into the electrolyte and further flows to the negative electrode, electrons are obtained at the negative electrode to form metal manganese which is coated on the surface of the negative electrode, so that the internal impedance of the battery is increased, and the discharge capacity of the battery is reduced.
CN 105762332a discloses a method for manufacturing a lithium ion battery, which uses a doped modified lithium manganate material as a positive electrode and a carbon-coated lithium titanate material as a negative electrode. The lithium manganate material is subjected to doping modification of aluminum and sulfur elements, so that the Jahn-Teller effect is inhibited; the carbon-coated lithium titanate material is used as the negative electrode, so that the defect that metal lithium dendrite is separated out due to too low graphite negative electrode potential is overcome, the discharge potential of the lithium manganate material is effectively limited, and the overall cycle performance of the battery is greatly improved. However, the anode of the invention is doped with aluminum and sulfur elements to inhibit the Jahn-Teller effect, but the valence state of the aluminum and the sulfur changes during the long-time operation of the battery, so that the inhibition effect on the Jahn-Teller effect is reduced, and the battery has poor long-time operation performance and limited cycle performance.
CN 103357557A discloses a method for continuously coating high-viscosity slurry for preparing a positive pole piece of a lithium-manganese primary battery, which comprises the steps of mixing electrolytic manganese dioxide subjected to heat treatment with conductive carbon black, and then adding deionized water or distilled water containing a polar alcohol solvent for continuously mixing to obtain a wet mixture; then adding an aqueous solution of a binder commonly used for lithium batteries and continuously mixing to obtain high-viscosity slurry; and preparing the high-viscosity mixed slurry into particles, rolling the particles by a coating roller to form continuous sheets, bonding the sheets on two sides of a current collector after rolling, continuously preparing a positive pole piece with uniform thickness, and performing drying, rolling, cutting and powder cleaning processes to obtain the required positive pole piece. The method improves the production efficiency and the product consistency, ensures the uniformity of the thickness of the material sheet, and improves the performance of the pole piece. The invention starts from the preparation process of the lithium manganese dioxide anode, and starts from the improvement of the thickness uniformity and the product consistency of the anode, but the physical regularity can improve the quality of the anode so as to improve the efficiency of the battery, but the invention can not fundamentally solve the Jahn-Teller effect caused by the change of the valence state of manganese and can not solve the problems of the increase of the internal resistance and the reduction of the efficiency of the battery in the working process of the battery.
Therefore, it is very important to research a lithium battery anode which can effectively inhibit the Jahn-Teller effect of the manganese element, reduce the internal resistance increasing rate in the working process of the battery and improve the working efficiency of the battery.
Disclosure of Invention
The invention provides a lithium battery anode, a lithium battery and a preparation method thereof, aiming at the problems that the inhibition effect of the Jahn-Teller effect of a manganese element in the lithium battery anode in the prior art is low and the problems that the internal resistance is increased and the battery efficiency is reduced in the working process of the battery cannot be effectively solved.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention aims to provide a lithium battery positive electrode, wherein the raw material of the lithium battery positive electrode comprises a manganese compound, and the raw material of the lithium battery positive electrode also comprises an aromatic acid lithium salt.
The following technical solutions are preferred but not limited to the technical solutions provided by the present invention, and the technical objects and advantages of the present invention can be better achieved and realized by the following technical solutions.
In a preferred embodiment of the present invention, the content of the lithium salt of an aromatic acid is 0.1 wt% to 1.0 wt%, for example, 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt%, 0.6 wt%, 0.7 wt%, 0.8 wt%, 0.9 wt%, or 1.0 wt%, but is not limited to the above-mentioned values, and other values not shown in the above-mentioned value range are also applicable, and preferably 0.2 wt% to 0.6 wt%.
Preferably, the lithium salt of an aromatic acid is selected from any one of lithium benzoate, lithium phenylacetate, lithium phthalate, lithium 2-picolinate, lithium α -naphthoate, lithium β -naphthoate or lithium 9-anthraceneformate or a combination of at least two of these, typical but non-limiting examples being: a combination of lithium benzoate and lithium phenylacetate, a combination of lithium benzoate and lithium phthalate, a combination of lithium benzoate and lithium 2-picolinate, a combination of lithium α -naphthoate and lithium β -naphthoate, a combination of lithium benzoate, lithium phenylacetate and lithium 9-anthraceneformate, or the like, preferably lithium benzoate.
In the discharging process of the lithium battery, the aromatic acid lithium salt effectively inhibits the Jahn-Teller effect of trivalent manganese in the positive electrode through the coordination effect, the stability of the trivalent manganese in the positive electrode is improved, and the quality of manganese dissolved in the electrolyte is reduced, so that the quality of Mn coated on the negative electrode is reduced, the internal resistance of the battery is reduced, and the working efficiency of the battery is improved.
Preferably, the manganese compound is selected from MnO2And/or LiMn2O4Preferably MnO2
As a preferred technical scheme of the invention, the lithium battery anode is mainly prepared from the following raw materials in percentage by mass:
Figure BDA0001143095950000031
Figure BDA0001143095950000041
the sum of the mass percentages of the raw materials is 100 wt%.
Wherein, the content of the manganese compound can be as follows: 85 wt%, 86 wt%, 87 wt%, 88 wt%, 89 wt%, 90 wt%, 91 wt%, 92 wt%, 93 wt%, 94 wt%, or 95 wt%, etc.; the content of the conductive carbon black may be: 0.5 wt%, 1 wt%, 1.5 wt%, 2 wt%, 2.5 wt%, 3 wt%, 3.5 wt%, 4 wt%, 4.5 wt%, or 5 wt%, etc.; the binder content may be: 3 wt%, 4 wt%, 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, 10 wt%, or the like; the content of the lithium salt of an aromatic acid may be: 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt%, 0.6 wt%, 0.7 wt%, 0.8 wt%, 0.9 wt%, or 1.0 wt%, etc.; however, the numerical values are not limited to the numerical values listed, and other numerical values not listed in the above numerical ranges are also applicable.
As a preferred technical scheme of the invention, the lithium battery anode is mainly prepared from the following raw materials in percentage by mass:
Figure BDA0001143095950000042
the sum of the mass percentages of the raw materials is 100 wt%.
As a preferred embodiment of the present invention, the conductive carbon black is selected from any one or a combination of at least two of acetylene black, graphite or ketjen black, and the combination is typically, but not limited to, exemplified by: a combination of acetylene black and graphite, a combination of acetylene black and ketjen black, a combination of graphite and ketjen black or a combination of acetylene black, graphite and ketjen black, preferably ketjen black.
Preferably, the binder is selected from any one or a combination of at least two of polytetrafluoroethylene, fluorinated ethylene propylene copolymer, polyvinylidene fluoride, polyacrylate or polyacrylonitrile, and the combination is exemplified by, but not limited to, a combination of polytetrafluoroethylene and fluorinated ethylene propylene copolymer, polytetrafluoroethylene and polyvinylidene fluoride, polytetrafluoroethylene and polyacrylate, polytetrafluoroethylene and polyacrylonitrile, polyvinylidene fluoride and polyacrylate, or polytetrafluoroethylene, polyvinylidene fluoride and polyacrylonitrile, and the like, and further preferably polytetrafluoroethylene.
Preferably, the thickness of the lithium battery positive electrode is 0.40 to 0.60mm, such as 0.40mm, 0.41mm, 0.42mm, 0.43mm, 0.44mm, 0.45mm, 0.48mm, 0.50mm, 0.52mm, 0.55mm, 0.58mm, or 0.60mm, but not limited to the values listed, and other values not listed included in the range of the values are also applicable, and more preferably 0.44 to 0.48 mm.
The invention also aims to provide a lithium battery, which comprises the lithium battery anode.
As a preferable technical scheme of the invention, the lithium battery mainly comprises the positive electrode, the negative electrode, the diaphragm and the electrolyte.
Preferably, the negative electrode is lithium, graphite or lithium titanate, further preferably lithium.
Preferably, the electrolyte includes a lithium salt and an organic solvent.
Preferably, the lithium salt is one or a combination of at least two of lithium perchlorate, lithium hexafluorophosphate or lithium tetrafluoroborate, typical but non-limiting examples of such combinations are: a combination of lithium perchlorate and lithium hexafluorophosphate, a combination of lithium perchlorate and lithium tetrafluoroborate, a combination of lithium hexafluorophosphate and lithium tetrafluoroborate or a combination of lithium perchlorate, lithium hexafluorophosphate and lithium tetrafluoroborate, and further preferably lithium perchlorate.
Preferably, the organic solvent is one or a combination of at least two of ethylene glycol dimethyl ether, 1, 3-dioxolane, tetrahydrofuran, ethylene carbonate, propylene carbonate or diethyl carbonate, typical but non-limiting examples of which are: a combination of ethylene glycol dimethyl ether and ethylene carbonate, a combination of 1, 3-dioxolane and propylene carbonate, a combination of propylene carbonate and diethyl carbonate, a combination of ethylene glycol dimethyl ether, 1, 3-dioxolane and propylene carbonate, or the like, and a combination of ethylene glycol dimethyl ether and propylene carbonate is more preferable.
According to the preferable technical scheme, the lithium battery is a lithium-manganese dioxide battery, the negative electrode of the lithium-manganese dioxide battery is lithium, and the electrolyte is a mixed solution of propylene carbonate and ethylene glycol dimethyl ether of lithium perchlorate.
Preferably, the volume ratio of the propylene carbonate to the ethylene glycol dimethyl ether in the mixed solution of the propylene carbonate and the ethylene glycol dimethyl ether is (0.25-4): 1, such as 0.25:1, 0.5:1, 0.7:1, 1:1, 1.5:1, 2:1, 2.5:1, 3:1, 3.5:1 or 4:1, but not limited to the enumerated values, and other non-enumerated values included in the numerical value range are also applicable, and more preferably (0.25-0.7): 1;
preferably, the lithium perchlorate is in a concentration of 0.1 to 5mol/L, such as 0.1mol/L, 0.2mol/L, 0.5mol/L, 1mol/L, 1.5mol/L, 2mol/L, 2.5mol/L, 3mol/L, 3.5mol/L, 4mol/L, 4.5mol/L, or 5mol/L, but not limited to the recited values, and other non-recited values included in the range of values are equally applicable; further preferably 0.5 to 2mol/L, particularly preferably 1 mol/L.
The invention also aims to provide a preparation method of the lithium battery, which comprises the following steps:
(1) mixing the raw materials of the lithium battery anode according to the formula amount to prepare a wet mass;
(2) pressing the wet mass obtained in the step (1) into a required thickness to obtain a positive electrode;
(3) and (3) assembling the positive electrode obtained in the step (2), the negative electrode, the diaphragm and the electrolyte into a lithium battery.
As the preferable technical scheme of the invention, the pressing method in the step (2) is to press the wet mass into a net by a film and then carry out fine pressing.
Preferably, after the wet mass is pressed in the step (2), cutting, removing powder and leading out the ear end are carried out.
Preferably, the positive electrode obtained in step (2) is dried before assembly.
Preferably, the temperature of the drying is 150 to 250 ℃, such as 150 ℃, 160 ℃, 170 ℃, 180 ℃, 190 ℃, 200 ℃, 210 ℃, 220 ℃, 230 ℃, 240 ℃ or 250 ℃, but not limited to the recited values, and other values not recited in the range of the values are also applicable, and more preferably 180 to 220 ℃.
Preferably, the drying time is 5 to 24 hours, such as 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, 12 hours, 15 hours, 18 hours, 20 hours, 22 hours or 24 hours, but not limited to the enumerated values, and other non-enumerated values included in the numerical range are also applicable, and more preferably 16 hours to 24 hours.
Compared with the prior art, the invention at least has the following beneficial effects:
(1) according to the lithium battery anode provided by the invention, by adding the aromatic acid lithium salt, in the discharging process of the battery, the Jahn-Teller effect of trivalent manganese in the anode is effectively inhibited, the stability of the trivalent manganese is improved, the amount of manganese dissolved in an electrolyte is reduced, and the amount of manganese covered on a cathode is further reduced;
(2) in the long-term high-temperature working process of the lithium battery, the internal resistance of the lithium battery is 50% -80% of that of a common lithium battery, and the working efficiency of the lithium battery is improved by nearly one time;
(3) the production method of the lithium battery provided by the invention has the advantages of simple process flow and simple and convenient operation, and can be used for industrial production of the lithium battery.
Drawings
FIG. 1 is a graph showing results of an alternating current impedance (ESI) test in an undischarged state of a lithium battery;
fig. 2 is a graph showing the results of an alternating current impedance (ESI) test in a state where a lithium battery is discharged by 75%.
The present invention is described in further detail below. The following examples are merely illustrative of the present invention and do not represent or limit the scope of the claims, which are defined by the claims.
Detailed Description
In order to better illustrate the present invention and facilitate the understanding of the technical solutions of the present invention, the present invention is further described in detail below. The following examples are merely illustrative of the present invention and do not represent or limit the scope of the claims, which are defined by the claims.
The embodiment of the invention provides a lithium battery positive electrode comprising a manganese compound, and the raw material of the lithium battery positive electrode also comprises an aromatic acid lithium salt. Meanwhile, a lithium battery assembled by the positive electrode, the negative electrode, the diaphragm and the electrolyte of the lithium battery and a preparation method of the lithium battery are provided.
Example 1
A lithium battery anode is composed of 88.4 wt% MnO25 wt% Ketjen black, 6 wt% polytetrafluoroethylene and 0.6 wt% lithium benzoate, and the thickness of the positive electrode is 0.45 mm.
Example 2
The positive electrode of the lithium battery consists of 85 wt% MnO24 wt% Ketjen black, 10 wt% polytetrafluoroethylene and 1 wt% lithium benzoate, and the thickness of the positive electrode is 0.44 mm.
Example 3
A lithium battery anode is composed of 88.6 wt% MnO25 wt% Ketjen black, 6 wt% polytetrafluoroethylene and 0.4 wt% lithium benzoate, and the thickness of the positive electrode is 0.45 mm.
Example 4
The lithium battery anode consists of 90 wt% MnO20.5 wt% Ketjen black, 9 wt% polytetrafluoroethylene, and 0.5 wt% lithium benzoate and lithium phenylacetate mixture (ratio of lithium benzoate to lithium phenylacetate mass: 1), with a positive electrode thickness of 0.40 mm.
Example 5
The lithium battery anode consists of 95 wt% MnO21.9 wt% Ketjen black, 3 wt% polytetrafluoroethylene, and 0.1 wt% lithium benzoate, and the thickness of the positive electrode is 0.60 mm.
Example 6
The anode of the lithium battery consists of 88 wt% MnO25 wt% of graphite, 6.4 wt% of polyacrylate and 0.6 wt% of lithium phenylacetate, and the thickness of the positive electrode is 0.45 mm.
Example 7
The anode of the lithium battery consists of 88 wt% MnO25 wt% acetylene black, 6.4 wt%Polyacrylonitrile and 0.6 wt% of lithium phthalate, and the thickness of the positive electrode is 0.45 mm.
Example 8
A lithium battery anode is composed of 88 wt% LiMn2O45 wt% Ketjen black, 6.4 wt% polytetrafluoroethylene, and 0.6 wt% lithium benzoate, and the thickness of the positive electrode is 0.45 mm.
Example 9
A lithium battery comprising the positive electrode for a lithium battery of example 1, the preparation method comprising the steps of:
(1) adding 88.4 wt% MnO2Mixing with Ketjen black 5 wt%, and mixing with polytetrafluoroethylene 6 wt% and lithium benzoate 0.6 wt% to obtain wet mass;
(2) screening the wet dough obtained in the step (1) through a pressed film, finely pressing to 0.45mm, cutting, removing powder, leading out an ear tip, and drying at 200 ℃ for 12 hours to obtain a positive electrode;
(3) and (3) assembling the anode, the cathode lithium, an electrolyte, namely a mixed solution of 1mol/L of propylene carbonate and ethylene glycol dimethyl ether of lithium perchlorate (the volume ratio of the propylene carbonate to the ethylene glycol dimethyl ether is 0.5:1), and a diaphragm into the lithium battery.
Example 10
A lithium battery comprising the positive electrode for a lithium battery of embodiment 2, the preparation method comprising the steps of:
(1) adding 85 wt% MnO2Mixing with 10 wt% Ketjen black, and mixing with 4% polytetrafluoroethylene and 1% lithium benzoate to obtain wet mass;
(2) screening the wet dough obtained in the step (1) through a pressed film, finely pressing to 0.44mm, cutting, removing powder, leading out an ear tip, and drying at 200 ℃ for 12 hours to obtain a positive electrode;
(3) and (3) assembling the anode and the cathode lithium obtained in the step (2), 1mol/L electrolyte of the propylene carbonate solution of lithium perchlorate and a diaphragm into a lithium battery.
Example 11
A lithium battery comprising the positive electrode for a lithium battery of embodiment 3, the preparation method comprising the steps of:
(1) Adding 88.6 wt% MnO2Fully mixing with 5 wt% of Ketjen black, and fully mixing with 6 wt% of polytetrafluoroethylene and 0.4 wt% of lithium benzoate to obtain wet mass;
(2) screening the wet dough obtained in the step (1) through a pressed film, finely pressing to 0.45mm, cutting, removing powder, leading out an ear tip, and drying at 200 ℃ for 12 hours to obtain a positive electrode;
(3) and (3) assembling the anode, the cathode lithium, an electrolyte, namely a mixed solution of 1mol/L of propylene carbonate and ethylene glycol dimethyl ether of lithium perchlorate (the volume ratio of the propylene carbonate to the ethylene glycol dimethyl ether is 0.5:1), and a diaphragm into the lithium battery.
Example 12
A lithium battery comprising the positive electrode for a lithium battery of embodiment 4, the preparation method comprising the steps of:
(1) adding 90 wt% MnO2Mixing with 0.5 wt% Ketjen black, and mixing with 9 wt% polytetrafluoroethylene and 0.5 wt% lithium benzoate and lithium phenylacetate to obtain wet mass;
(2) screening the wet dough obtained in the step (1) through a pressed film, finely pressing to 0.40mm, cutting, removing powder, leading out an ear tip, and drying at 150 ℃ for 24 hours to obtain a positive electrode;
(3) and (3) assembling the positive electrode and the negative electrode obtained in the step (2), electrolyte, namely 0.1mol/L ethylene carbonate solution of lithium tetrafluoroborate, and a diaphragm into a lithium battery.
Example 13
A lithium battery comprising the positive electrode for a lithium battery of embodiment 5, the preparation method comprising the steps of:
(1) adding 95 wt% MnO2Mixing with 1.9 wt% Ketjen black, and mixing with 3 wt% polytetrafluoroethylene and 0.1 wt% lithium benzoate to obtain wet mass;
(2) screening the wet dough obtained in the step (1) through a pressed film, finely pressing to 0.60mm, cutting, removing powder, leading out an ear tip, and drying at 250 ℃ for 5 hours to obtain a positive electrode;
(3) and (3) assembling the positive electrode and the negative electrode obtained in the step (2), an electrolyte, namely 5mol/L diethyl carbonate solution of lithium hexafluorophosphate, and a diaphragm into a lithium battery.
Example 14
A lithium battery comprising the positive electrode for a lithium battery of embodiment 6, the preparation method comprising the steps of:
(1) adding 88 wt% MnO2Mixing with Ketjen black 5 wt%, and mixing with polytetrafluoroethylene 6.4 wt% and lithium phenylacetate 0.6 wt% to obtain wet mass;
(2) screening the wet dough obtained in the step (1) through a pressed film, finely pressing to 0.45mm, cutting, removing powder, leading out an ear tip, and drying at 200 ℃ for 12 hours to obtain a positive electrode;
(3) and (3) assembling the anode, the cathode lithium, an electrolyte, namely a mixed solution of 1mol/L of propylene carbonate and ethylene glycol dimethyl ether of lithium perchlorate (the volume ratio of the propylene carbonate to the ethylene glycol dimethyl ether is 0.5:1), and a diaphragm into the lithium battery.
Example 15
A lithium battery comprising the positive electrode for a lithium battery of example 7, the preparation method comprising the steps of:
(1) adding 88 wt% MnO2Fully mixing with 5 wt% of Ketjen black, and fully mixing with 6.4 wt% of polytetrafluoroethylene and 0.6 wt% of lithium phthalate to prepare wet mass;
(2) screening the wet dough obtained in the step (1) through a pressed film, finely pressing to 0.45mm, cutting, removing powder, leading out an ear tip, and drying at 200 ℃ for 12 hours to obtain a positive electrode;
(3) and (3) assembling the anode, the cathode lithium, an electrolyte, namely a mixed solution of 1mol/L of propylene carbonate and ethylene glycol dimethyl ether of lithium perchlorate (the volume ratio of the propylene carbonate to the ethylene glycol dimethyl ether is 0.5:1), and a diaphragm into the lithium battery.
Example 16
A preparation method of a lithium battery comprises the following steps:
(1) mixing 88 wt% LiMn2O4Mixing with Ketjen black 5 wt%, and mixing with polytetrafluoroethylene 6.4 wt% and lithium benzoate 0.6 wt% to obtain wet mass;
(2) screening the wet dough obtained in the step (1) through a pressed film, finely pressing to 0.45mm, cutting, removing powder, leading out an ear tip, and drying at 200 ℃ for 12 hours to obtain a positive electrode;
(3) and (3) assembling the anode obtained in the step (2), the cathode lithium titanate, an electrolyte, namely a mixed solution of 1mol/L of propylene carbonate and ethylene glycol dimethyl ether of lithium perchlorate (the volume ratio of the propylene carbonate to the ethylene glycol dimethyl ether is 0.5:1), and a diaphragm into the lithium battery.
Example 17
A lithium battery and a method for preparing the same, the method comprising the steps of:
(1) mixing 88 wt% LiMn2O4Fully mixing with 5 wt% of Ketjen black, and fully mixing with 6.4 wt% of polypropylene carbonate and 0.6 wt% of lithium benzoate to obtain a wet mass;
(2) pressing the wet mass obtained in the step (1) on a net by a pressing film, finely pressing to 0.48mm, cutting, removing powder, leading out an ear tip, and drying at 200 ℃ for 12h to obtain a positive electrode;
(3) and (3) assembling the anode obtained in the step (2), the cathode graphite, 1mol/L lithium tetrafluoroborate 1, 3-dioxolane solution as electrolyte and a diaphragm into a lithium battery.
Example 18
A lithium battery and a method for preparing the same, the method comprising the steps of:
(1) mixing 88 wt% LiMn2O4Fully mixing with 5 wt% of Ketjen black, and fully mixing with 6.4 wt% of polyacrylonitrile and 0.6 wt% of lithium benzoate to obtain wet mass;
(2) screening the wet dough obtained in the step (1) through a pressed film, finely pressing to 0.60mm, cutting, removing powder, leading out an ear tip, and drying at 200 ℃ for 12 hours to obtain a positive electrode;
(3) and (3) assembling the positive electrode obtained in the step (2), negative electrode graphite, electrolyte, namely 1mol/L diethyl carbonate solution of lithium hexafluorophosphate, and a diaphragm into a lithium battery.
Example 19
Except that the mixed solution of propylene carbonate and ethylene glycol dimethyl ether (the volume ratio of propylene carbonate to ethylene glycol dimethyl ether is 0.25:1) of 1mol/L lithium perchlorate in the step (3), the conditions of the lithium battery are the same as those of the embodiment 9
Example 20
Except that in the step (3), a mixed solution of 1mol/L of propylene carbonate and ethylene glycol dimethyl ether of lithium perchlorate (the volume ratio of the propylene carbonate to the ethylene glycol dimethyl ether is 4:1), the other conditions are the same as those in the embodiment 9
Comparative example 1
This comparative example provides a lithium battery under the same conditions as example 9 except that lithium benzoate was not added to the positive electrode of the lithium battery.
Comparative example 2
This comparative example provides a lithium battery under the same conditions as example 11 except that lithium benzoate was not added to the positive electrode of the lithium battery.
Comparative example 3
This comparative example provides a lithium battery under the same conditions as example 14 except that lithium phenylacetate was not added to the positive electrode of the lithium battery.
Comparative example 4
This comparative example provides a lithium battery under the same conditions as example 15 except that lithium phthalate was not added to the positive electrode of the lithium battery.
Comparative example 5
This comparative example provides a lithium battery under the same conditions as example 16 except that lithium benzoate was not added to the positive electrode of the lithium battery.
The lithium batteries of examples 9, 11, 14, 15 and 16 and any of comparative examples 1 to 5 were subjected to an alternating current impedance (ESI) test, after being discharged (0%) and 75%, respectively, under the following test conditions: under the open circuit voltage, the test frequency is 10mHZ-100KHZ, the alternating current amplitude is 5mV, and the test result is subjected to data fitting analysis by using a SIM in an alternating current impedance tester. The test results are shown in the following table.
TABLE 1
As can be seen from the comparison of the above table, the lithium battery with the positive electrode added with the aromatic acid lithium salt has a small semicircular impedance difference compared with the lithium battery without the positive electrode added with the aromatic acid lithium salt in a non-discharge (0%) state; however, in the state of 75% discharge, the internal resistance of the lithium battery with the added aromatic acid lithium salt at the positive electrode is obviously lower than that of the lithium battery without the added aromatic acid lithium salt at the positive electrode, and the pulse voltage is higher than that of the lithium battery without the added aromatic acid lithium salt at the positive electrode. Therefore, in the discharging process of the lithium battery, the aromatic acid lithium salt effectively inhibits the Jahn-Teller effect of the trivalent manganese in the positive electrode through the coordination effect, the stability of the trivalent manganese in the positive electrode is improved, and the quality of manganese dissolved in the electrolyte is reduced, so that the quality of Mn coated on the negative electrode is reduced, the internal resistance of the battery is reduced, and the working efficiency of the battery is improved.
The applicant declares that the present invention illustrates the detailed structural features of the present invention through the above embodiments, but the present invention is not limited to the above detailed structural features, that is, it does not mean that the present invention must be implemented depending on the above detailed structural features. It should be understood by those skilled in the art that any modifications of the present invention, equivalent substitutions of selected components of the present invention, additions of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.

Claims (36)

1. The positive electrode of the lithium battery is characterized in that the positive electrode of the lithium battery also comprises an aromatic acid lithium salt;
the lithium battery anode is mainly prepared from the following raw materials in percentage by mass:
Figure FDA0002214019550000011
the sum of the mass percentages of the raw materials is 100 wt%.
2. The positive electrode for a lithium battery according to claim 1, wherein the lithium salt of an aromatic acid is contained in an amount of 0.2 to 0.6 wt%.
3. The positive electrode of claim 1, wherein the aromatic lithium salt is selected from any one of lithium benzoate, lithium phenylacetate, lithium phthalate, lithium 2-picolinate, lithium α -naphthoate, lithium β -naphthoate, or lithium 9-anthraceneformate, or a combination of at least two thereof.
4. The positive electrode for a lithium battery according to claim 3, wherein the lithium salt of an aromatic acid is lithium benzoate.
5. The positive electrode for lithium batteries according to claim 1, wherein said manganese compound is selected from the group consisting of MnO2And/or LiMn2O4
6. The positive electrode for lithium battery as claimed in claim 5, wherein the manganese compound is MnO2
7. The lithium battery positive electrode as claimed in claim 1, which is prepared from the following raw materials in percentage by mass:
Figure FDA0002214019550000012
Figure FDA0002214019550000021
the sum of the mass percentages of the raw materials is 100 wt%.
8. The positive electrode for lithium battery according to claim 1, wherein the conductive carbon black is selected from any one of acetylene black, graphite or ketjen black or a combination of at least two thereof.
9. The positive electrode for a lithium battery as claimed in claim 8, wherein the conductive carbon black is ketjen black.
10. The positive electrode for a lithium battery as claimed in claim 1, wherein the binder is selected from any one or a combination of at least two of polytetrafluoroethylene, fluorinated ethylene propylene copolymer, polyvinylidene fluoride, polyacrylate, or polyacrylonitrile.
11. The positive electrode for a lithium battery as claimed in claim 10, wherein the binder is polytetrafluoroethylene.
12. The positive electrode for a lithium battery as claimed in claim 1, wherein the positive electrode for a lithium battery has a thickness of 0.40 to 0.60 mm.
13. The positive electrode for a lithium battery as claimed in claim 12, wherein the positive electrode for a lithium battery has a thickness of 0.44 to 0.48 mm.
14. A lithium battery comprising a positive electrode for a lithium battery as claimed in any one of claims 1 to 13.
15. The lithium battery of claim 14, wherein the lithium battery consists of the positive electrode, the negative electrode, a separator, and an electrolyte.
16. The lithium battery of claim 15, wherein the negative electrode is lithium, graphite, or lithium titanate.
17. The lithium battery of claim 16, wherein the negative electrode is lithium.
18. The lithium battery of claim 15, wherein the electrolyte comprises a lithium salt and an organic solvent.
19. The lithium battery of claim 18, wherein the lithium salt is selected from any one of or a combination of at least two of lithium perchlorate, lithium hexafluorophosphate, or lithium tetrafluoroborate.
20. The lithium battery of claim 19, wherein the lithium salt is lithium perchlorate.
21. The lithium battery of claim 18, wherein the organic solvent is selected from any one of ethylene glycol dimethyl ether, 1, 3-dioxolane, tetrahydrofuran, ethylene carbonate, propylene carbonate, or diethyl carbonate, or a combination of at least two thereof.
22. The lithium battery of claim 21, wherein the organic solvent is a mixed solvent system of propylene carbonate and ethylene glycol dimethyl ether.
23. The lithium battery of claim 14, wherein the lithium battery is a lithium-manganese dioxide battery, the negative electrode of the lithium-manganese dioxide battery is lithium, and the electrolyte is a mixed solution of propylene carbonate and ethylene glycol dimethyl ether of lithium perchlorate.
24. The lithium battery as claimed in claim 23, wherein the volume ratio of propylene carbonate to ethylene glycol dimethyl ether in the mixed solution of propylene carbonate and ethylene glycol dimethyl ether is (0.25-4): 1.
25. The lithium battery of claim 24, wherein the volume ratio of propylene carbonate to ethylene glycol dimethyl ether in the mixed solution of propylene carbonate and ethylene glycol dimethyl ether is (0.25-0.7): 1.
26. The lithium battery as claimed in claim 23, wherein the concentration of the lithium perchlorate is 0.1 to 5 mol/L.
27. The lithium battery as claimed in claim 26, wherein the concentration of the lithium perchlorate is 0.5 to 2 mol/L.
28. The lithium battery of claim 27, wherein the concentration of lithium perchlorate is 1 mol/L.
29. A method for manufacturing a lithium battery as claimed in any one of the claims 14 to 28, characterized in that the method comprises the following steps:
(1) mixing the raw materials of the lithium battery anode according to the formula amount to prepare a wet mass;
(2) pressing the wet mass into a required thickness to obtain a positive electrode;
(3) and assembling the positive electrode, the negative electrode, the diaphragm and the electrolyte into the lithium battery.
30. The method of claim 29, wherein said pressing in step (2) is performed by passing said wet dough through a wire and then coining.
31. The method of claim 29 wherein the wet mass is pressed to a desired thickness in step (2) and then further subjected to cutting, dusting and extraction of the terminal ears.
32. The method of claim 29, wherein the positive electrode of step (3) is dried prior to assembly.
33. The method of claim 32, wherein the drying temperature is 150-250 ℃.
34. The method of claim 33, wherein the drying temperature is 180-220 ℃.
35. The method of claim 32, wherein the drying time is 5-24 hours.
36. The method of claim 35, wherein the drying time is 16-24 hours.
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