CN108155384B - Inorganic binder lithium ion battery - Google Patents

Inorganic binder lithium ion battery Download PDF

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CN108155384B
CN108155384B CN201711405103.6A CN201711405103A CN108155384B CN 108155384 B CN108155384 B CN 108155384B CN 201711405103 A CN201711405103 A CN 201711405103A CN 108155384 B CN108155384 B CN 108155384B
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binder
active material
lithium
lithium ion
ion battery
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CN108155384A (en
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顾庆文
夏永高
刘兆平
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Ningbo Fuli Battery Material Technology Co Ltd
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Ningbo Fuli Battery Material Technology Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • 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
    • 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
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/665—Composites
    • H01M4/667—Composites in the form of layers, e.g. coatings
    • 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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  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
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  • Manufacturing & Machinery (AREA)
  • Composite Materials (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Secondary Cells (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)

Abstract

The invention belongs to the field of batteries, and particularly relates to an inorganic binder lithium ion battery. The positive electrode of the lithium ion battery provided by the invention comprises a current collector and an active material layer coated on the current collector; the active material layer includes a positive electrode active material, a conductive agent, and a binder; the binder comprises a mixture of sodium silicate and lithium silicate. The lithium ion battery provided by the invention adopts the inorganic silicate as the binder of the positive active material, so that the battery has good cycling stability, and the service life of the battery is greatly prolonged. And the inorganic silicate is soluble in water, so that the use of an organic solvent can be avoided when the battery is prepared, and potential safety hazards and environmental pollution existing when the battery is prepared by using the organic solvent are eliminated.

Description

Inorganic binder lithium ion battery
Technical Field
The invention belongs to the field of batteries, and particularly relates to an inorganic binder lithium ion battery.
Background
The lithium ion battery has the advantages of no memory effect, high safety, high specific energy, low self-discharge rate and the like, is widely applied to the field of mobile equipment, notebook computers and mobile phone communication, and is very suitable for the field of hybrid electric vehicles and electric vehicles.
The binding agent is an important component of the anode of the lithium ion battery, and has the main functions of combining an anode active material, a conductive agent and a current collector, stabilizing a pole piece structure, buffering volume change in the charging and discharging process of the battery, maintaining the stability of an electrode structure and ensuring that the electrode material can repeatedly release and embed lithium. The failure of the binder can cause the loss of conductive connection among different components of the battery anode, and partial anode active material particles are insulated and cannot participate in charge and discharge, thereby causing the reduction of the electrochemical performance of the battery. Therefore, it is important to select a suitable adhesive.
Currently, in the industrial production of lithium ion batteries, the commonly used binder is an organic solvent type polyvinylidene fluoride (PVDF), such as N-methylpyrrolidone (NMP) solution of PVDF. However, the cycling stability of the lithium ion battery prepared by using the binder is still to be improved, and the organic solvent NMP is volatile, has high toxicity, is flammable and explosive, seriously pollutes the environment and harms the health of operators in a production workshop. Therefore, in order to meet the development trend of the green industry, the search for a novel green binder capable of replacing the organic solvent type PVDF has important and profound significance.
Disclosure of Invention
In view of the above, the present invention is directed to an inorganic binder lithium ion battery, which does not need to use organic solvent PVDF as a binder and has more excellent cycle stability.
The invention provides a lithium ion battery, wherein a positive electrode of the lithium ion battery comprises a current collector and an active substance layer coated on the current collector;
the active material layer includes a positive electrode active material, a conductive agent, and a binder;
the binder comprises a mixture of sodium silicate and lithium silicate.
Preferably, the general formula of the mixture of sodium silicate and lithium silicate is represented by formula (I):
(Na1-XLiX)2O·nSiO2formula (I);
in the formula (I), x is more than or equal to 0.1 and less than or equal to 0.5, and n is 1, 2 or 3.
Preferably, the mixture of sodium silicate and lithium silicate is prepared according to the following method:
and mixing the silicon dioxide, the lithium carbonate and the sodium carbonate, and sintering to obtain a mixture of sodium silicate and lithium silicate.
Preferably, the positive electrode active material includes LiNi0.5Mn1.5O4、LiNi0.8Co0.15Al0.05O2、LiMn2O4、LiFePO4、LiCoO2、Li(NiCoMn)O2、Li[Li0.144Ni0.136Co0.136Mn0.544]O2And LiFeO4One or more of (a).
Preferably, the conductive agent includes one or more of graphite, acetylene black, conductive graphite, graphene, carbon fiber, carbon nanotube, and ketjen black.
Preferably, the mass ratio of the positive electrode active material, the conductive agent and the binder in the active material layer is (60-100): (1-20): (1-20).
Preferably, the mass ratio of the positive electrode active material, the conductive agent and the binder in the active material layer is (75-85): (5-10): (5-10).
Preferably, the thickness of the active material layer is 20 to 30 μm.
Preferably, the current collector includes an aluminum foil or a copper foil.
Preferably, the positive electrode is prepared according to the following method:
mixing a positive electrode active material, a conductive agent, a binder and a solvent to obtain active substance slurry; and coating the active substance slurry on a current collector, and drying to obtain the anode.
The invention provides an application of a mixture of sodium silicate and lithium silicate as a binder in preparation of a lithium ion battery anode.
Compared with the prior art, the invention provides an inorganic binder lithium ion battery. The positive electrode of the lithium ion battery provided by the invention comprises a current collector and an active material layer coated on the current collector; the active material layer includes a positive electrode active material, a conductive agent, and a binder; the binder comprises a mixture of sodium silicate and lithium silicate. The lithium ion battery provided by the invention adopts the inorganic silicate as the binder of the positive active material, so that the battery has good cycling stability, and the service life of the battery is greatly prolonged. And the inorganic silicate is soluble in water, so that the use of an organic solvent can be avoided when the battery is prepared, and potential safety hazards and environmental pollution existing when the battery is prepared by using the organic solvent are eliminated.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
Fig. 1 is a diagram of the charge and discharge performance of the button cell prepared in example 1 of the present invention;
FIG. 2 is a comparison graph of the charge-discharge cycle performance of button cells prepared according to example 1 of the present invention and comparative example;
fig. 3 is a graph comparing the rate discharge performance of button cells prepared in examples 1 and 2 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a lithium ion battery, wherein a positive electrode of the lithium ion battery comprises a current collector and an active substance layer coated on the current collector;
the active material layer includes a positive electrode active material, a conductive agent, and a binder;
the binder comprises a mixture of sodium silicate and lithium silicate.
The lithium ion battery provided by the invention comprises a positive electrode, a negative electrode, a diaphragm between the positive electrode and the negative electrode and electrolyte. Wherein the positive electrode includes a current collector and an active material layer coated on the current collector. In the present invention, the current collector includes, but is not limited to, aluminum foil or copper foil; the thickness of the current collector is preferably 12-17 μm, and specifically can be 15 μm.
In the present invention, the active material layer of the positive electrode includes a positive electrode active material, a conductive agent, and a binder; the positive active material includes LiMn2O4、LiFePO4、LiCoO2、LiNi0.5Mn1.5O4、LiNi0.8Co0.15Al0.05O2、Li(NiCoMn)O2、Li[Li0.144Ni0.136Co0.136Mn0.544]O2And LiFeO4One or more of; the Li (NiCoMn) O2Preferred are the three types NCM811, NCM622, NCM523, NCM433 and NCM333One or more of the meta-materials.
In the present invention, the conductive agent in the active material layer includes, but is not limited to, one or more of graphite, acetylene black, conductive graphite, graphene, carbon fiber, carbon nanotube, and ketjen black; the graphite is preferably one or more of KS-6, KS-15, SFG-6 and SFG-6 in type; the conductive graphite is preferably Super P and/or Super S.
In the present invention, the binder in the active material layer comprises a mixture of sodium silicate and lithium silicate, the general formula of which is represented by formula (I): (Na)1-XLiX)2O·nSiO2Formula (I); in the formula (I), x is more than or equal to 0.1 and less than or equal to 0.5, x can be 0.1, 0.2, 0.3, 0.4 or 0.5, and n is 1, 2 or 3. In one embodiment provided by the present invention, the mixture of sodium silicate and lithium silicate may specifically be (Na)0.5Li0.5)2O·SiO2、(Na0.8Li0.2)2O·SiO2、(Na0.6Li0.4)2O·2SiO2、(Na0.6Li0.4)2O·3SiO2、(Na0.9Li0.1)2O·1SiO2、(Na0.7Li0.3)2O·2SiO2、(Na0.5Li0.5)2O·2SiO2、(Na0.8Li0.2)2O·3SiO2Or (Na)0.9Li0.1)2O·3SiO2. In the present invention, the mixture of sodium silicate and lithium silicate may be prepared as follows:
and mixing the silicon dioxide, the lithium carbonate and the sodium carbonate, and sintering to obtain a mixture of sodium silicate and lithium silicate.
In the method for preparing the mixture of sodium silicate and lithium silicate provided by the present invention, the ratio of the amount of silicon dioxide, lithium carbonate and sodium carbonate is not particularly limited, and those skilled in the art can select the ratio of the amount of silicon dioxide, lithium carbonate and sodium carbonate according to the chemical formula of the desired mixture of sodium silicate and lithium silicate; the mixing mode of the silicon dioxide, the lithium carbonate and the sodium carbonate is preferably ball milling; the sintering temperature is preferably 1000-1250 ℃, and specifically can be 1000 ℃, 1050 ℃, 1100 ℃, 1150 ℃, 1200 ℃ or 1250 ℃; the sintering time is preferably 12-15 h, and specifically can be 12h, 13h, 14h or 15 h. After sintering, the mixture of sodium silicate and lithium silicate of the invention can be obtained by crushing.
In the invention, the mass ratio of the positive electrode active material, the conductive agent and the binder in the active material layer is preferably (60-100): (1-20): (1-20), more preferably (75-85): (5-10): (5-10), specifically 80:10:10, 90:5:5, 70:15:15, 80:15:15, 60:20:20, 85:10:5, 75:15:10, 70:20:10, 90:7:3 or 75:12.5: 12.5. In the present invention, the thickness of the active material layer is preferably 20 to 30 μm, more preferably 22 to 26 μm, and specifically 22 μm, 23 μm, 24 μm, 25 μm, or 26 μm.
In the invention, the positive electrode can be prepared according to the following method:
mixing a positive electrode active material, a conductive agent, a binder and a solvent to obtain active substance slurry; and coating the active substance slurry on a current collector, and drying to obtain the anode.
In the above method for producing a positive electrode, the solvent is preferably water; the binder accounts for preferably 0.1-10%, more preferably 0.6-8%, most preferably 1-6%, most preferably 2-4%, and specifically can be 2%, 2.5% or 3% of the total mass of the binder and the solvent; the mixing mode is preferably that firstly, the binder and the solvent are mixed to obtain a binder solution, and then the positive active material, the conductive agent and the binder solution are mixed; the drying mode is preferably drying; the drying temperature is preferably 40-120 ℃, and more preferably 80-100 ℃.
The selection of the negative electrode has no special requirement, and the negative electrode which is known in the field and can be used for a lithium ion battery can be adopted; in one embodiment provided herein, the negative electrode is a lithium sheet.
The selection of the diaphragm is not specially required, and the diaphragm which is known in the field and can be used for a lithium ion battery can be adopted; in one embodiment provided by the present invention, the separator is a polypropylene microporous membrane Celgard 2400.
The selection of the electrolyte has no special requirement, and the electrolyte which is known in the field and can be used for a lithium ion battery can be adopted; in one embodiment provided by the invention, the electrolyte is 1M LiPF6The solvent is a mixed solution of Ethylene Carbonate (EC) and dimethyl carbonate (DMC) in a volume ratio of 1: 1.
The preparation method of the lithium ion battery provided by the invention is not particularly limited, and the lithium ion battery can be assembled by adopting an assembly mode known by the technical personnel in the field to assemble the positive electrode, the negative electrode, the diaphragm and the electrolyte.
The lithium ion battery provided by the invention adopts the inorganic silicate as the binder of the positive active material, so that the battery has good cycling stability, and the service life of the battery is greatly prolonged. And the inorganic silicate is soluble in water, so that the use of an organic solvent can be avoided when the battery is prepared, and potential safety hazards and environmental pollution existing when the battery is prepared by using the organic solvent are eliminated.
The invention also provides the application of the mixture of sodium silicate and lithium silicate as a binder in the preparation of the anode of the lithium ion battery. In the application provided by the invention, the inorganic silicate is used as the binder of the positive active material, so that the battery has good cycling stability, and the service life of the battery is greatly prolonged. And the inorganic silicate is soluble in water, so that the use of an organic solvent can be avoided when the battery is prepared, and potential safety hazards and environmental pollution existing when the battery is prepared by using the organic solvent are eliminated.
For the sake of clarity, the following examples are given in detail.
Example 1
In this example, the lithium ion battery positive electrode active material binder used was a mixture of sodium silicate and lithium silicate (Na)0.5Li0.5)2O·SiO2The lithium ion battery anode using the adhesive comprises a current collector aluminum foil and an active substance layer coated on the surface of the current collector aluminum foil, wherein the active substance layer comprises a lithium-rich manganese basePositive electrode active material Li [ Li ]0.144Ni0.136Co0.136Mn0.544]O2Conductive agent Super P and adhesive (Na)0.5Li0.5)2O·SiO2The preparation method of the lithium ion battery anode comprises the following steps:
mixing silicon dioxide, lithium carbonate and sodium carbonate according to the proportion of 1: 1: mixing solid phase at a molar ratio of 1, sintering at 1200 deg.C for 13 hr, and pulverizing to obtain binder (Na)0.5Li0.5)2O·SiO2. Mixing the binder with water to obtain (Na) with a mass solubility of 2.5%0.5Li0.5)2O·SiO2Aqueous solution according to Li [ Li ] as positive electrode active material rich in lithium manganese0.144Ni0.136Co0.136Mn0.544]O2Conductive agent Super P and adhesive (Na)0.5Li0.5)2O·SiO2Preparing the lithium-rich manganese-based positive electrode active material, the conductive agent and the binder aqueous solution into active substance slurry according to the mass ratio of 80:10: 10. And (3) uniformly coating the prepared active substance slurry on 15-micron Al foil after vacuum defoaming, performing vacuum drying at 80 ℃ for 12 hours to form a 23-micron active substance layer, and rolling and slitting to obtain the lithium ion battery anode.
Transferring the dried positive plate into a glove box, taking a lithium plate as a negative electrode, taking a polypropylene microporous membrane Celgard2400 as a diaphragm and taking 1MLiPF6/[ Ethylene Carbonate (EC) + dimethyl carbonate (DMC) in a 1:1 volume ratio]2025 button cells were assembled as electrolyte.
The charge and discharge performance of the first loop of the button cell prepared in the embodiment 1 of the invention is tested at 25 ℃ under the test temperature, the voltage range of 2.0-4.8V and the charge and discharge current density of 0.1C (30mA/g), the test result is shown in figure 1, and figure 1 is a graph of the charge and discharge performance of the first loop of the button cell prepared in the embodiment 1 of the invention.
The charge-discharge cycle performance of the button cell prepared in the embodiment 1 of the invention is tested at the test temperature of 25 ℃, the voltage range is 2.0-4.8V, the charge-discharge current density is 0.1C and 0.2C, the test result is shown in figure 2, and figure 2 is a comparison graph of the charge-discharge cycle performance of the button cell prepared in the embodiment 1 of the invention and the button cell prepared in the comparative example. As can be seen from fig. 2, after the button cell provided by this embodiment is subjected to 100 cycles of charge and discharge, the 0.2C specific discharge capacity is still as high as 264.6ma.h/g, which shows good cycle stability.
The rate discharge performance of the button cell prepared in example 1 of the present invention was tested at 25 ℃ under a test temperature and a voltage range of 2.0-4.8V, and the result is shown in fig. 3, where fig. 3 is a comparison graph of the rate discharge performance of the button cell prepared in example 1 and example 2 of the present invention. As can be seen from fig. 3, the button cell provided by the present embodiment exhibits excellent rate performance.
Comparative example
In comparative example, the binder used for the positive active material of the lithium ion battery was polyvinylidene fluoride (PVDF). The positive electrode of the lithium ion battery using the binder is the same as the positive electrode active material and the conductive agent in example 1, and the manufacturing method is the same as the manufacturing method in example 1.
Mixing PVDF and N-methylpyrrolidone (NMP) to obtain an NMP solution of PVDF with the mass solubility of 2.5%, and adopting a lithium-rich manganese-based positive electrode active material Li [ Li ]0.144Ni0.136Co0.136Mn0.544]O2And preparing the lithium-rich manganese-based positive electrode active material, the conductive agent and the binder solution into active substance slurry according to the mass ratio of the Super P to the PVDF of 80:10: 10. And (3) uniformly coating the prepared active substance slurry on an aluminum foil with the thickness of 15 mu m after vacuum defoaming, performing vacuum drying for 12 hours at the temperature of 80 ℃ to form an active substance layer with the thickness of 23 mu m, and rolling and slitting to obtain the lithium ion battery anode.
Transferring the dried positive plate into a glove box, taking a lithium plate as a negative electrode, taking a polypropylene microporous membrane Celgard2400 as a diaphragm and taking 1MLiPF6/[ Ethylene Carbonate (EC) + dimethyl carbonate (DMC) in a 1:1 volume ratio]2025 button cells were assembled as electrolyte.
The charge-discharge cycle performance of the button cell prepared by the comparative example of the invention is tested at 25 ℃ under the test temperature, the voltage range of 2.0-4.8V, the charge-discharge current density of 0.1C and the charge-discharge current density of 0.2C, and the test result is shown in figure 2. Fig. 2 is a comparison graph of the charge and discharge cycle performance of the button cell prepared in example 1 of the present invention and the comparative example. As can be seen from fig. 2, after 100 cycles of charge and discharge, the button cell prepared in the comparative example has a specific discharge capacity at 0.2C rate of only 197.1ma.h/g, which is much lower than that of example 1. Experiments show that the mixture of sodium silicate and lithium silicate is used as the binder, so that the cycling stability of the lithium ion battery is obviously improved, and the service life of the battery is greatly prolonged.
Example 2
In this example, the lithium ion battery positive electrode active material binder used was a mixture of sodium silicate and lithium silicate (Na)0.8Li0.2)2O·SiO2The lithium ion battery anode using the binder comprises a current collector aluminum foil and an active material layer coated on the surface of the current collector aluminum foil, wherein the active material layer comprises a lithium-rich anode active material Li [ Li ]0.144Ni0.136Co0.136Mn0.544]O2Conductive agent Super P and adhesive (Na)0.8Li0.2)2O·SiO2The preparation method of the lithium ion battery anode comprises the following steps:
mixing silicon dioxide, lithium carbonate and sodium carbonate according to the proportion of 5: 2: mixing solid phase at 8 mol ratio, sintering at 1250 deg.C for 15 hr, and pulverizing to obtain binder (Na)0.8Li0.2)2O·SiO2. Mixing binder and water to obtain (Na) with mass solubility of 15%0.8Li0.2)2O·SiO2Aqueous solution according to Li [ Li ] as positive electrode active material rich in lithium manganese0.144Ni0.136Co0.136Mn0.544]O2And the Super P and the binder are prepared into active substance slurry by the lithium-rich manganese-based positive active material, the conductive agent and the binder aqueous solution according to the mass ratio of 90:5: 5. And (3) uniformly coating the prepared active substance slurry on an aluminum foil with the thickness of 15 microns after vacuum defoaming, performing vacuum drying at the temperature of 80 ℃ for 12 hours to form an active substance layer with the thickness of 23 microns, and rolling and slitting to obtain the lithium ion battery anode.
Transferring the dried positive plate into a glove box, taking a lithium plate as a negative electrode, taking a polypropylene microporous membrane Celgard2400 as a diaphragm and taking 1MLiPF6Volume ratio of Ethylene Carbonate (EC) + dimethyl carbonate (DMC) 1:1]2025 button cells were assembled as electrolyte.
The charge-discharge cycle performance of the button cell prepared in the embodiment 2 of the invention is tested under the test temperature of 25 ℃, the voltage range of 2.0-4.8V and the charge-discharge current density of 0.1C (30mA/g), after 50 cycles of charge-discharge cycle, the discharge specific capacity is still as high as 260.8Ma.h/g, which shows that (Na) is used0.8Li0.2)2O·SiO2As Li [ Li ]0.144Ni0.136Co0.136Mn0.544]O2Lithium ion batteries with positive active material binders exhibit good cycling stability.
The rate discharge performance of the button cell prepared in example 2 of the present invention was tested at 25 ℃ under a test temperature and a voltage range of 2.0-4.8V, and the result is shown in fig. 3, where fig. 3 is a comparison graph of the rate discharge performance of the button cell prepared in example 1 and example 2 of the present invention. As can be seen from fig. 3, the button cell provided by the present embodiment exhibits excellent rate performance.
Example 3
In this example, the lithium ion battery positive electrode active material binder used was a mixture of sodium silicate and lithium silicate (Na)0.6Li0.4)2O·2SiO2The lithium ion battery anode using the binder comprises a current collector aluminum foil and an active material layer coated on the surface of the current collector aluminum foil, wherein the active material layer comprises a lithium-rich anode active material Li [ Li ]0.144Ni0.136Co0.136Mn0.544]O2Conductive agent Super P and adhesive (Na)0.6Li0.4)2O·2SiO2The preparation method of the lithium ion battery anode comprises the following steps:
mixing silicon dioxide, lithium carbonate and sodium carbonate according to the proportion of 5: 4: mixing solid phase at 3 mol ratio, sintering at 1200 deg.C for 14 hr, and pulverizing to obtain binder (Na)0.6Li0.4)2O·2SiO2. Mixing binder and water to obtain (Na) with mass solubility of 2%0.6Li0.4)2O·2SiO2Aqueous solution according to Li [ Li ] as positive electrode active material rich in lithium manganese0.144Ni0.136Co0.136Mn0.544]O2Super P and adhesive bondingThe mass ratio of the lithium-rich manganese-based positive electrode active material to the conductive agent to the binder is 70:15:15, and the active material slurry is prepared from the lithium-rich manganese-based positive electrode active material, the conductive agent and the binder aqueous solution. And (3) uniformly coating the prepared active substance slurry on an aluminum foil with the thickness of 15 mu m after vacuum defoaming, performing vacuum drying for 12 hours at the temperature of 80 ℃ to form an active substance layer with the thickness of 22 mu m, and rolling and slitting to obtain the lithium ion battery anode.
Transferring the dried positive plate into a glove box, taking a lithium plate as a negative electrode, taking a polypropylene microporous membrane Celgard2400 as a diaphragm and taking 1MLiPF6Volume ratio of Ethylene Carbonate (EC) + dimethyl carbonate (DMC) 1:1]2025 button cells were assembled as electrolyte.
The charge-discharge cycle performance of the button cell prepared in the embodiment 3 of the invention is tested under the test temperature of 25 ℃, the voltage range of 2.0-4.8V and the charge-discharge current density of 0.1C (30mA/g), after 50 cycles of charge-discharge cycle, the discharge specific capacity is still 254.6mA.h/g, which indicates that the battery is used (Na)0.6Li0.4)2O·2SiO2As Li [ Li ]0.144Ni0.136Co0.136Mn0.544]O2Lithium ion batteries with positive active material binders exhibit good cycling stability.
Example 4
In this example, the lithium ion battery positive electrode active material binder used was a mixture of sodium silicate and lithium silicate (Na)0.6Li0.4)2O·3SiO2The lithium ion battery anode using the binder comprises a current collector aluminum foil and an active material layer coated on the surface of the current collector aluminum foil, wherein the active material layer comprises a lithium-rich anode active material Li [ Li ]0.144Ni0.136Co0.136Mn0.544]O2Conductive agent Super P and adhesive (Na)0.6Li0.4)2O·3SiO2The preparation method of the lithium ion battery anode comprises the following steps:
mixing silicon dioxide, lithium carbonate and sodium carbonate according to the weight ratio of 15: 6: mixing solid phase at 4 mol ratio, sintering at 1200 deg.C for 12 hr, and pulverizing to obtain binder (Na)0.6Li0.4)2O·3SiO2. Mixing a binder and water to obtain a mixture with a mass solubility of3% of (Na)0.6Li0.4)2O·3SiO2Aqueous solution according to Li [ Li ] as positive electrode active material rich in lithium manganese0.144Ni0.136Co0.136Mn0.544]O2And preparing the lithium-rich manganese-based positive electrode active material, a conductive agent and a binder aqueous solution into active substance slurry according to the mass ratio of the Super P to the binder of 60:20: 20. And (3) uniformly coating the prepared active substance slurry on an aluminum foil with the thickness of 15 mu m after vacuum defoaming, performing vacuum drying for 12 hours at the temperature of 80 ℃ to form an active substance layer with the thickness of 23 mu m, and rolling and slitting to obtain the lithium ion battery anode.
Transferring the dried positive plate into a glove box, taking a lithium plate as a negative electrode, taking a polypropylene microporous membrane Celgard2400 as a diaphragm and taking 1MLiPF6Volume ratio of Ethylene Carbonate (EC) + dimethyl carbonate (DMC) 1:1]2025 button cells were assembled as electrolyte.
The charge-discharge cycle performance of the button cell prepared in comparative example 4 of the present invention was tested at 25 ℃ under the test temperature, voltage range of 2.0-4.8V, and charge-discharge current density of 0.1C (30mA/g), and after 50 cycles of charge-discharge cycle, the specific discharge capacity was still up to 246.2ma.h/g, indicating that (Na) was used0.6Li0.4)2O·3SiO2As Li [ Li ]0.144Ni0.136Co0.136Mn0.544]O2Lithium ion batteries with positive active material binders exhibit good cycling stability.
Example 5
In this example, the binder (Na) for the positive electrode active material of the lithium ion battery0.9Li0.1)2O·1SiO2The lithium ion battery anode using the binder comprises a current collector aluminum foil and an active material layer coated on the surface of the current collector aluminum foil, wherein the active material layer comprises an anode active material (LiMn)2O4) Conductive agent KS-6 and binder (Na)0.9Li0.1)2O·1SiO2The preparation method of the lithium ion battery anode comprises the following steps:
mixing silicon dioxide, lithium carbonate and sodium carbonate according to the proportion of 5: 9: mixing the solid phase with 1 mol ratio, sintering at 1200 ℃ for 13h, crushing,to obtain a binder (Na)0.9Li0.1)2O·1SiO2. Mixing binder and water to obtain (Na) with mass solubility of 2%0.9Li0.1)2O·1SiO2And (2) preparing an aqueous solution, namely preparing a lithium manganate positive electrode active material, KS-6 and a binder according to a mass ratio of 85:10: and 5, preparing the positive active material, the conductive agent and the binder aqueous solution into active material slurry. And (3) uniformly coating the prepared active substance slurry on an aluminum foil with the thickness of 15 mu m after vacuum defoaming, performing vacuum drying for 12 hours at the temperature of 90 ℃ to form an active substance layer with the thickness of 23 mu m, and rolling and slitting to obtain the lithium ion battery anode.
Transferring the dried pole piece into a glove box, taking a lithium piece as a negative electrode, taking a polypropylene microporous membrane Celgard2400 as a diaphragm, and taking 1MLiPF6Volume ratio of Ethylene Carbonate (EC) + dimethyl carbonate (DMC) 1:1]2025 button cells were assembled as electrolyte.
The charge-discharge cycle performance of the button cell prepared in example 5 of the present invention was tested at 25 ℃ under the conditions of test temperature, voltage range of 3.0-4.4V, 10C charging current density, and 1C discharging current density, and the results showed that (Na) was used0.9Li0.1)2O·1SiO2As LiMn2O4After 300 cycles of charge and discharge, the capacity retention rate of the lithium ion battery with the positive electrode active material binder is 92%, and good cycle stability is shown. In addition, the binder in the embodiment takes water as a solvent, so that the use of organic solvents is greatly reduced, and further, the harm to the environment and human bodies is reduced.
Example 6
In this example, the binder (Na) for the positive electrode active material of the lithium ion battery0.7Li0.3)2O·2SiO2The lithium ion battery anode using the binder comprises a current collector aluminum foil and an active material layer coated on the surface of the current collector aluminum foil, wherein the active material layer comprises an anode active material (LiFeO)4) Conductive agent Super P and adhesive (Na)0.7Li0.3)2O·2SiO2The preparation method of the lithium ion battery anode comprises the following steps:
mixing silica with a solventLithium carbonate and sodium carbonate according to a weight ratio of 10: 3: mixing solid phase at 7 mol ratio, sintering at 1200 deg.C for 13 hr, and pulverizing to obtain binder (Na)0.7Li0.3)2O·2SiO2. Mixing binder and water to obtain (Na) with mass solubility of 3%0.7Li0.3)2O·2SiO2Aqueous solution according to LiFeO4The mass ratio of the positive active material, the conductive agent Super P and the adhesive sodium silicate is 75:15:10 preparing the positive active material, the conductive agent and the binder aqueous solution into active material slurry. And (3) uniformly coating the prepared active substance slurry on an aluminum foil with the thickness of 15 mu m after vacuum defoaming, performing vacuum drying for 12 hours at the temperature of 100 ℃ to form an active substance layer with the thickness of 26 mu m, and rolling and slitting to obtain the lithium ion battery anode.
Transferring the dried positive plate into a glove box, taking a lithium plate as a negative electrode, taking a polypropylene microporous membrane Celgard2400 as a diaphragm, and taking 1M LiPF6Volume ratio of Ethylene Carbonate (EC) + dimethyl carbonate (DMC) 1:1]2025 button cells were assembled as electrolyte.
The charge-discharge cycle performance of the button cell prepared in example 6 of the present invention was tested at 25 ℃ under the conditions of test temperature, voltage range of 3.0-4.4V, 2C charging current density, and 10C discharging current density, and the results showed that (Na) was used0.7Li0.3)2O·2SiO2As LiFeO4After the lithium ion battery with the positive electrode active material binder is subjected to charge-discharge cycle for 400 circles, the capacity retention rate is 85%, and good cycle stability is shown. In addition, the binder in the embodiment takes water as a solvent, so that the use of organic solvents is greatly reduced, and further, the harm to the environment and human bodies is reduced.
Example 7
In this example, the binder (Na) for the positive electrode active material of the lithium ion battery0.5Li0.5)2O·2SiO2The lithium ion battery anode using the adhesive comprises a current collector aluminum foil and an active substance layer coated on the surface of the current collector aluminum foil, wherein the active substance layer comprises LiNi0.8Co0.15Al0.05O2(NCA) Positive electrode active Material, conductive agent Super P and Binder (Na)0.5Li0.5)2O·2SiO2The preparation method of the lithium ion battery anode comprises the following steps:
mixing silicon dioxide, lithium carbonate and sodium carbonate according to the proportion of 2: 1: mixing solid phase at a molar ratio of 1, sintering at 1185 deg.C for 13 hr, and pulverizing to obtain binder (Na)0.5Li0.5)2O·2SiO2. Mixing binder and water to obtain (Na) with mass solubility of 3%0.5Li0.5)2O·2SiO2Aqueous solution according to LiNi0.8Co0.15Al0.05O2(NCA) Positive electrode active Material, Super P and Binder (Na)0.5Li0.5)2O·2SiO2And preparing the positive active material, the conductive agent and the binder aqueous solution into active substance slurry according to the mass ratio of 80:15: 5. And (3) uniformly coating the prepared active substance slurry on an aluminum foil with the thickness of 15 microns after vacuum defoaming, performing vacuum drying for 12 hours at the temperature of 110 ℃ to form an active substance layer with the thickness of 25 microns, and rolling and slitting to obtain the lithium ion battery anode.
Transferring the dried positive plate into a glove box, taking a lithium plate as a negative electrode, taking a polypropylene microporous membrane Celgard2400 as a diaphragm, and taking 1M LiPF6Volume ratio of Ethylene Carbonate (EC) + dimethyl carbonate (DMC) 1:1]2025 button cells were assembled as electrolyte.
The charge-discharge cycle performance of the button cell prepared in example 7 of the present invention was tested at 25 ℃ under the conditions of test temperature, voltage range of 3.0-4.4V, 10C charging current density, and 1C discharging current density, and the results showed that (Na) was used0.5Li0.5)2O·2SiO2After 100 cycles of charge and discharge, the capacity retention rate of the lithium ion battery serving as the NCA positive electrode active material binder is 97%, and good cycle stability is shown. In addition, the binder in the embodiment takes water as a solvent, so that the use of organic solvents is greatly reduced, and further, the harm to the environment and human bodies is reduced.
Example 8
In this example, the binder (Na) for the positive electrode active material of the lithium ion battery0.8Li0.2)2O·3SiO2Use the adhesiveThe lithium ion battery anode with the bonding agent comprises a current collector aluminum foil and an active substance layer coated on the surface of the current collector aluminum foil, wherein the active substance layer comprises a ternary anode active material NCM523, a conductive agent Super P and a bonding agent (Na)0.8Li0.2)2O·3SiO2The preparation method of the lithium ion battery anode comprises the following steps:
mixing silicon dioxide, lithium carbonate and sodium carbonate according to the weight ratio of 15: 2: mixing solid phase at 4 mol ratio, sintering at 1130 deg.C for 15 hr, and pulverizing to obtain binder (Na)0.8Li0.2)2O·3SiO2. Mixing binder and water to obtain (Na) with mass solubility of 3%0.8Li0.2)2O·3SiO2And preparing the active material slurry from the aqueous solution of the positive active material, the conductive agent and the binder according to the mass ratio of the ternary positive active material NCM523 to the Super P to the binder of 70:20: 10. And (3) uniformly coating the prepared active substance slurry on an aluminum foil with the thickness of 15 mu m after vacuum defoaming, performing vacuum drying for 12 hours at the temperature of 80 ℃ to form an active substance layer with the thickness of 22 mu m, and rolling and slitting to obtain the lithium ion battery anode.
Transferring the dried positive plate into a glove box, taking a lithium plate as a negative electrode, taking a polypropylene microporous membrane Celgard2400 as a diaphragm, and taking 1M LiPF6Volume ratio of Ethylene Carbonate (EC) + dimethyl carbonate (DMC) 1:1]2025 button cells were assembled as electrolyte.
The charge-discharge cycle performance of the button cell prepared in the embodiment 8 of the present invention was tested under the conditions of 25 ℃ test temperature, voltage range of 3.0-4.4V, 10C charging current density, and 1C discharging current density, and the results show that (Na) is used0.8Li0.2)2O·3SiO2After 100 cycles of charge and discharge cycles, the capacity retention rate of the lithium ion battery serving as the NCM523 positive electrode active material binder was 83%, and good cycle stability was exhibited. In addition, the binder in the embodiment takes water as a solvent, so that the use of organic solvents is greatly reduced, and further, the harm to the environment and human bodies is reduced.
Example 9
In this example, the binder of the positive active material of the lithium ion battery(Na0.9Li0.1)2O·3SiO2The lithium ion battery anode using the adhesive comprises a current collector aluminum foil and an active substance layer coated on the surface of the current collector aluminum foil, wherein the active substance layer comprises spinel LiNi0.5Mn1.5O4Positive electrode active material, conductive agent Super P and binder (Na)0.9Li0.1)2O·3SiO2The preparation method of the lithium ion battery anode comprises the following steps:
mixing silicon dioxide, lithium carbonate and sodium carbonate according to the weight ratio of 15: 1: mixing the solid phase with 9 mol ratio, sintering at 1250 deg.C for 15h, and pulverizing to obtain binder (Na)0.9Li0.1)2O·3SiO2. Mixing the binder with water to obtain (Na) with a mass solubility of 2.5%0.9Li0.1)2O·3SiO2Aqueous solution, according to spinel LiNi0.5Mn1.5O4And preparing active material slurry from the positive active material, the Super P and the binder according to the mass ratio of 90:7: 3. And (3) uniformly coating the prepared active substance slurry on an aluminum foil with the thickness of 15 mu m after vacuum defoaming, performing vacuum drying for 12 hours at the temperature of 80 ℃ to form an active substance layer with the thickness of 24 mu m, and rolling and slitting to obtain the lithium ion battery anode.
Transferring the dried positive plate into a glove box, taking a lithium plate as a negative electrode, taking a polypropylene microporous membrane Celgard2400 as a diaphragm and taking 1MLiPF6Volume ratio of Ethylene Carbonate (EC) + dimethyl carbonate (DMC) 1:1]2025 button cells were assembled as electrolyte.
The charge-discharge cycle performance of the button cell prepared in example 9 was tested at 25 ℃ under a test temperature, a voltage range of 3.0-4.4V and a charge-discharge current density of 1C, and the results show that (Na) was used0.9Li0.1)2O·3SiO2As LiNi0.5Mn1.5O4After 100 cycles of charge and discharge, the capacity retention rate of the lithium ion battery with the positive electrode active material binder is 97%, and good cycle stability is shown. In addition, the binder in the embodiment takes water as a solvent, so that the use of organic solvents is greatly reduced, and further, the use of organic solvents is reducedReducing the harm to the environment and human body.
Example 10
In this example, the binder of the positive electrode active material of the lithium ion battery was (Na)0.5Li0.5)2O·2SiO2The lithium ion battery anode using the binder comprises a current collector aluminum foil and an active material layer coated on the surface of the current collector aluminum foil, wherein the active material layer comprises a lithium-rich manganese-based anode active material Li [ Li ]0.144Ni0.136Co0.136Mn0.544]O2Conductive agent Super P and adhesive (Na)0.5Li0.5)2O·2SiO2The preparation method of the lithium ion battery anode comprises the following steps:
mixing silicon dioxide, lithium carbonate and sodium carbonate according to the proportion of 2: 1: mixing solid phase at 1 mol ratio, sintering at 1150 deg.C for 12 hr, and pulverizing to obtain binder (Na)0.5Li0.5)2O·2SiO2. Mixing the binder with water to obtain (Na) with a mass solubility of 2.5%0.5Li0.5)2O·2SiO2Aqueous solution according to Li [ Li ] as positive electrode active material rich in lithium manganese0.144Ni0.136Co0.136Mn0.544]O2And preparing the lithium-rich manganese-based positive electrode active material, a conductive agent and a binder aqueous solution into active substance slurry according to the mass ratio of the Super P to the binder of 75:12.5: 12.5. And (3) uniformly coating the prepared active substance slurry on an aluminum foil with the thickness of 15 mu m after vacuum defoaming, performing vacuum drying for 12 hours at the temperature of 80 ℃ to form an active substance layer with the thickness of 25 mu m, and rolling and slitting to obtain the lithium ion battery anode.
Transferring the dried positive plate into a glove box, taking a lithium plate as a negative electrode, taking a polypropylene microporous membrane Celgard2400 as a diaphragm and taking 1MLiPF6Volume ratio of Ethylene Carbonate (EC) + dimethyl carbonate (DMC) 1:1]2025 button cells were assembled as electrolyte.
The charge-discharge cycle performance of the button cell prepared in example 10 was tested at 25 ℃ with a test temperature and a voltage range of 2.0-4.8V and 0.1C (30mA/g), and the results show that (Na) was used0.5Li0.5)2O·2SiO2As Li[Li0.144Ni0.136Co0.136Mn0.544]O2After 50 cycles of charge and discharge, the specific discharge capacity of the lithium ion battery with the positive active material binder is still 263.5mAh/g, which shows that the lithium ion battery using the modified sodium silicate as the binder shows good cycle stability.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (4)

1. A lithium ion battery, its positive pole includes the current collector and active material layer coated on said current collector;
the active material layer includes a positive electrode active material, a conductive agent, and a binder;
the binder comprises a mixture of sodium silicate and lithium silicate;
the general formula of the mixture of sodium silicate and lithium silicate is shown as the formula (I):
(Na1-XLiX)2O·nSiO2formula (I);
in the formula (I), x is more than or equal to 0.1 and less than or equal to 0.5, and n is 1, 2 or 3.
2. The battery according to claim 1, wherein the mixture of sodium silicate and lithium silicate is prepared by the following method:
and mixing the silicon dioxide, the lithium carbonate and the sodium carbonate, and sintering to obtain a mixture of sodium silicate and lithium silicate.
3. The lithium ion battery according to claim 1, wherein the mass ratio of the positive electrode active material, the conductive agent and the binder in the active material layer is (60-100): (1-20): (1-20).
4. The mixture of sodium silicate and lithium silicate is used as a binder for preparing the anode of the lithium ion battery;
the general formula of the mixture of sodium silicate and lithium silicate is shown as the formula (I):
(Na1-XLiX)2O·nSiO2formula (I);
in the formula (I), x is more than or equal to 0.1 and less than or equal to 0.5, and n is 1, 2 or 3.
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