CN113113605A - Network structure ion conductive adhesive and preparation method and application thereof - Google Patents
Network structure ion conductive adhesive and preparation method and application thereof Download PDFInfo
- Publication number
- CN113113605A CN113113605A CN202110304080.XA CN202110304080A CN113113605A CN 113113605 A CN113113605 A CN 113113605A CN 202110304080 A CN202110304080 A CN 202110304080A CN 113113605 A CN113113605 A CN 113113605A
- Authority
- CN
- China
- Prior art keywords
- network structure
- adhesive
- pluronic
- aqueous solution
- conductive adhesive
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
- H01M4/622—Binders being polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a network structure ion conductive adhesive, a preparation method and application thereof, wherein the adhesive is synthesized by a one-pot method, the preparation process is simple, the adhesive combines the excellent adhesion performance of polyacrylic acid to active materials and the good ion conductivity of polyoxyethylene polyoxypropylene ether segmented copolymer chain segments, and a three-dimensional cross-linked network structure is formed by condensation reaction. When the lithium ion battery anode is applied to a lithium ion battery cathode, the problem of electrode structure degradation in the charging and discharging process can be effectively solved, and the electrochemical performance of the electrode is improved; the three-dimensional network structure enables the adhesive to have excellent mechanical properties, and can effectively relieve stress generated by the active material in the charging and discharging processes; the ion conductivity provides a lithium ion migration channel for the electrode, so that the transportation of lithium ions is promoted, and the method has important significance for improving the rate capability of the electrode.
Description
Technical Field
The invention belongs to the technical field of energy batteries, and particularly relates to a network structure ion conductive adhesive as well as a preparation method and application thereof.
Background
With the rapid development of social economy, the traditional fossil energy sources such as coal, petroleum and the like cannot meet the requirements of people in the current times on energy development due to the defects of non-regeneration, limited reserves, serious pollution and the like. Therefore, effective development and large-scale utilization of green, clean, safe and efficient new energy technology have important significance for relieving energy and environmental crisis faced by human beings and sustainable development of future human society.
The lithium ion battery, as a novel green chargeable and dischargeable energy storage device, has the advantages of high energy density, high operating voltage, long service life, environmental friendliness and the like, and is widely applied to electronic equipment such as mobile phones and notebook computers. In recent years, in response to the trend of miniaturization and thinning of electronic products, lithium ion batteries are more and more required to meet the market demand. Moreover, as many countries declare that consumption and sale of fuel vehicles are stopped in the future, development of new energy electric vehicles, which are large-scale energy storage applications, becomes a trend, and higher requirements are put forward on performance of lithium ion batteries.
The binder, which is a key component for maintaining the structure of an electrode in a battery, mainly functions to adhere an electrode active material and a conductive agent to a current collector, and the quality of the performance thereof directly affects the electrochemical performance of the electrode. Particularly, for alloy negative electrode materials such as silicon, tin, antimony, germanium and the like with huge volume expansion in the lithium intercalation process, the volume change of the electrode material in the charge-discharge process is adapted by selecting a polymer adhesive with controllable design structure and performance, so that the method is a simple and effective method for improving the cycling stability of the electrode.
The most common polymer binder in the preparation of electrodes of commercial lithium ion batteries at present is polyvinylidene fluoride (PVDF), which has a linear structure and no functionalized branched structure, can be combined with a negative electrode material only by van der waals force, and cannot provide enough adhesive force, so that the electrode material is easily pulverized and falls off from a current collector, the performance of the battery is unstable, and the capacity is rapidly attenuated. Sodium carboxymethyl cellulose (CMC) and polyacrylic acid (PAA) can be connected with the electrode material through chemical bonds, and the binding force is strong, so that the cycling stability of the electrode is relatively improved. They are still linear structures and difficult to adapt to various challenges caused by the large volume expansion of the anode material. Therefore, the development of a novel functional binder is urgently needed to solve the key technical problem, so that the application of the alloy negative electrode material in the lithium ion battery is promoted.
Disclosure of Invention
The invention aims to provide a polyacrylic acid-pluronic adhesive with a network structure and ion conductivity as well as a preparation method and application thereof, so as to overcome the defects in the prior art; the functional polymer network adhesive prepared by a one-pot method is prepared by the condensation reaction of polyacrylic acid and pluronic which are prepared by directly carrying out free radical reaction polymerization on acrylic monomers in an aqueous medium. The adhesive is formed by crosslinking polyacrylic acid and pluronic so as to form a network structure, so that the bonding force between the adhesive and an active material can be improved, the integrity and the stability of an electrode structure can be effectively maintained, and the circulating stability of an electrode can be improved; meanwhile, the polyoxyethylene and polyoxypropylene chain segments of the pluronic have ion conductivity, so that a lithium ion migration channel can be provided, and the rate capability of the electrode can be improved.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a network structure ion conductive adhesive comprises the following steps:
step 1: dissolving pluronic in deionized water to prepare a pluronic water solution; dissolving an acrylic acid monomer in deionized water to prepare an acrylic acid aqueous solution, and adding lithium hydroxide powder to adjust the pH value of the acrylic acid aqueous solution;
step 2: adding an initiator into the acrylic acid aqueous solution with the pH value adjusted, heating the acrylic acid aqueous solution to 60-90 ℃, and adding the pluronic aqueous solution prepared in the step 1;
and step 3: and (3) magnetically stirring the reaction solution obtained in the step (2), reacting under the protection of nitrogen, and finishing the reaction after reacting for 1-5h to obtain the network structure ion conductive adhesive formed by crosslinking polyacrylic acid and pluronic.
Furthermore, the chain segment of the pluronic is polyoxyethylene polyoxypropylene ether, has ion conductivity, can provide an ion migration channel, and improves the rate capability of the electrode.
Further, in the step 1, the mass concentration of the pluronic water solution is 5% -30%;
in the step 2, the mass concentration of the acrylic acid aqueous solution is 25-50%, and lithium hydroxide powder is added to adjust the pH value of the acrylic acid aqueous solution to 5-7.
Further, the initiator is any one of ammonium persulfate and sodium metabisulfite, and the using amount of the initiator is 0.05-2% of the mass of the acrylic monomer.
Further, the mass ratio of the acrylic acid monomer to the pluronic is (7-9): (1-3), the acrylic acid monomer and the pluronic are subjected to dehydration condensation reaction after free radical polymerization, meanwhile, high molecular chain entanglement can also exist, and hydrogen bond interaction exists between the polyacrylic acid and the pluronic, so that a cross-linked network structure is formed.
The network structure ion conductive adhesive is prepared by the preparation method of the network structure ion conductive adhesive. The polyoxypropylene block in the pluronic molecule can improve the stability of the electrode slurry through hydrophobic effect, and the network structure formed by crosslinking polyacrylic acid and pluronic can improve the adhesion of the electrode, so that the cycle performance of the electrode is improved.
An application of a network structure ion conductive adhesive in preparation of a secondary battery negative electrode is characterized in that a negative electrode active material and a conductive additive are dispersed in a network structure ion conductive adhesive aqueous solution, uniformly mixed slurry is obtained through ball milling, the slurry is uniformly coated on a copper foil current collector, and the secondary battery negative electrode is obtained after vacuum drying.
Furthermore, the mass concentration of the network structure ion conductive adhesive aqueous solution is 5%, and the absolute dry mass ratio of the negative electrode active material, the conductive additive and the network structure ion conductive adhesive is (60-95): (4.5-25): 0.5-15).
Further, the negative active material is selected from carbon materials and composite materials thereof, silicon-based materials and composite materials thereof, and phosphorus-based materials and composite materials thereof; the conductive additive is a composite conductive additive formed by mixing carbon black, carbon nano tubes, carbon fibers or two of the carbon black, the carbon nano tubes and the carbon fibers.
Further, the temperature of the vacuum drying is 80-120 ℃, and the drying time is 2-10 h; the network structure ion conductive adhesive can bond a negative electrode material, a conductive additive and a copper current collector and can also stabilize SEI (solid electrolyte interphase) of a battery negative electrode.
Compared with the prior art, the invention has the following beneficial technical effects:
the invention also provides a preparation method of the network structure ionic conduction adhesive, which is a polyacrylic acid-pluronic adhesive with a three-dimensional cross-linking network structure and ionic conduction inferior performance prepared by a one-pot method, and is prepared by the condensation reaction of polyacrylic acid (PAA) which is directly polymerized by acrylic acid monomers in a water medium through a free radical reaction and is condensed with pluronic with a polyoxyethylene polyoxypropylene ether block copolymer as a chain segment. The adhesive prepared by the method is a water-based adhesive, and is environment-friendly and good in safety in the preparation and use processes; the whole preparation process has simple flow, short reaction time and high preparation efficiency; and the adhesive has the advantages of easily obtained raw materials, low cost, good repeatability and wide application in actual production.
The invention provides a network structure ion conductive polyacrylic acid-pluronic adhesive, which forms a three-dimensional cross-linked network structure by pluronic condensation of polyacrylic acid (PAA) and a block copolymer with polyoxyethylene polyoxypropylene ether, and has higher mechanical strength and good tensile property. In addition, polyoxyethylene and polyoxypropylene are well-known ion conductive materials, and lithium ions are coordinated and combined with oxygen atoms containing lone pair electrons in chain segments to form a migration channel of the lithium ions, so that the transportation of the lithium ions is effectively promoted. Therefore, the pluronic is used as a synthetic raw material, so that the synthetic adhesive has good ion conductivity, a three-dimensional network structure capable of conducting ions is formed, the large-volume expansion of negative electrode materials such as silicon, tin, antimony and germanium in the lithium embedding process can be well limited, and the cycle performance and the rate capability of the lithium ion battery are further improved. The adhesive can also be used as the adhesive of positive electrode materials such as lithium iron phosphate, lithium cobaltate and the like, and can also be used for coating ceramic diaphragms.
The invention also discloses application of the network structure ion conductive adhesive, which can be used for preparing a secondary battery cathode. The polyacrylic acid chain in the adhesive contains a large number of carboxyl (-COOH) groups, and can form covalent bonds and hydrogen bonds with the surface of an active material, so that the adhesive force of the adhesive is enhanced. Meanwhile, the three-dimensional cross-linked network structure of the adhesive has excellent mechanical properties, can effectively adapt to volume change of an electrode in the charging and discharging process, relieves internal stress generated by volume effect, and maintains the integrity and stability of the electrode structure. In addition, the polyoxyethylene polyoxypropylene ether segmented copolymer segment in the adhesive not only endows the adhesive with good ion conductivity, but also provides a lithium ion migration channel for an electrode, and improves the rate capability of the electrode; and also eliminates the decrease in ion conductivity due to crystallization, as compared with a simple polyoxyethylene segment. Verification shows that the charge-discharge cycle performance of the lithium ion battery cathode using the adhesive is obviously improved, and the specific expression is that the capacity of the battery is still stable along with the increase of the number of cycles, and meanwhile, the rate performance of the battery is greatly improved. The electrode still has a complete structure after continuous charge and discharge cycles, almost no cracks are generated, and the thickness change of the electrode is small.
Drawings
Fig. 1 is a graph showing the peel strength of an electrode sheet prepared in example 12 of the present invention;
fig. 2 is a scanning electron microscope image before and after the cycle of the electrode sheet prepared in example 2 of the present invention; wherein, (a) is before circulation and (b) is after circulation;
fig. 3 is a graph comparing rate performance of nano-silicon negative electrode cells assembled by electrode tabs prepared in example 1 of the present invention and electrode tabs prepared in comparative example 1.
Detailed Description
Embodiments of the invention are described in further detail below:
an ion conductive adhesive with a network structure is prepared by polymerizing acrylic acid monomers into polyacrylic acid (PAA) through a free radical reaction in an aqueous medium, and then performing a condensation reaction with Pluronic with a segment of polyoxyethylene polyoxypropylene ether block copolymer to form a three-dimensional cross-linked network structure; meanwhile, Polyoxyethylene (PEO) and polyoxypropylene (PPO) are well known ion conductive materials to provide the synthesized binder with good ion conductive properties. The pluronic chain segment is polyoxyethylene polyoxypropylene ether block copolymer.
A preparation method of a network structure ion conductive adhesive comprises the following steps:
step 1, preparing a pluronic aqueous solution, adding pluronic into deionized water, and stirring to completely dissolve the pluronic to prepare the pluronic aqueous solution with the mass concentration of 5% -30%;
step 2, adding an acrylic acid monomer into deionized water, stirring to completely dissolve the acrylic acid monomer to obtain an acrylic acid aqueous solution with the mass concentration of 25-50%, and adding lithium hydroxide powder to adjust the pH value of the acrylic acid aqueous solution to 5-7; the mass ratio of the acrylic acid monomer (AA) to the pluronic is (7-9): (1-3);
step 3, adding an initiator into the acrylic acid solution, wherein the initiator is a compound which is easy to be thermally decomposed into free radicals and is any one of ammonium persulfate or sodium metabisulfite, and the using amount of the initiator is 0.05-2% of the mass of the acrylic acid monomer;
and 4, heating the solution in which the acrylic acid and the initiator are dissolved to 60-90 ℃, then dropwise adding the pluronic solution into the solution, reacting under the protection of nitrogen and magnetic stirring, wherein the reaction temperature is 60-90 ℃, and finishing the reaction after the reaction is carried out for 1-5 hours, thereby preparing the adhesive.
The adhesive is a network structure ion conductive adhesive, has a three-dimensional cross-linked network structure and good ion conductivity, simultaneously shows excellent mechanical properties, has good elasticity and high strength, can bear huge volume expansion of an electrode active material in a lithium embedding process, and effectively maintains the stability of an electrode structure.
The lithium ion battery cathode can be prepared on the basis of the network structure ion conductive adhesive, the cathode comprises a copper foil current collector, and a cathode active material, a conductive additive and an adhesive which are attached to the current collector, and the preparation process comprises the following steps: dispersing a negative electrode active material and a conductive additive in a network structure ion conductive adhesive aqueous solution with the mass concentration of 5%, and performing ball milling in a planetary ball mill for 1h to obtain uniformly mixed slurry, wherein the mass ratio of the negative electrode active material, the conductive additive and the network structure ion conductive adhesive is (60-95): 4.5-25): 0.5-15, and the negative electrode active material is selected from a carbon material and a composite material thereof, a silicon material and a composite material thereof, and a phosphorus material and a composite material thereof; the conductive additive is carbon black, carbon nano tubes, carbon fibers or a composite conductive additive formed by mixing two of the carbon black, the carbon nano tubes and the carbon fibers; and then, uniformly coating the slurry on a copper foil current collector by using an automatic film coating machine, and carrying out vacuum drying for 2-10h at the temperature of 80-120 ℃ to obtain the secondary battery cathode.
When the negative electrode is used for assembling a lithium ion half cell for testing, the electrode is made of lithium metal; the electrolyte is a mixed solution of lithium hexafluorophosphate, dimethyl carbonate and diethyl carbonate, and contains 10 vol% of fluoroethylene carbonate (FEC) as an additive; the diaphragm is a polypropylene microporous diaphragm; wherein the concentration of lithium hexafluorophosphate in the electrolyte is 1 mol/L.
The preparation method of the lithium ion button cell comprises the following steps: cutting the negative electrode of the secondary battery by using a manual punching machine to obtain an electrode slice with the diameter of 12 mm. It was then transferred to a super clean glove box filled with argon for assembly of a 2032 type button half cell.
The tests for lithium ion button cells were as follows: and (3) placing the prepared 2032 button half-cell for 6h, then starting to test, and carrying out constant current charge-discharge cycle test on the cell by using a blue cell test system under the voltage range of 0.01-1.5V or 0.01-2V.
The present invention is described in further detail below with reference to examples:
comparative example 1
Preparing a lithium ion battery nano silicon negative electrode by using a polyacrylic acid adhesive (the theoretical specific capacity is 4000 mAh/g): mixing the following components in percentage by weight of 70:15:15, mixing the nano silicon particles, Super-P conductive carbon black and a polyacrylic acid (PAA) aqueous solution, and carrying out ball milling in a planetary ball mill for 1h to fully mix the mixture to obtain uniformly dispersed negative electrode slurry; and coating the slurry on a copper foil current collector by using an automatic film coating agent, wherein the coating thickness is 25 mu m, and drying the copper foil current collector for 2h under vacuum at 100 ℃ to obtain the final electrode. And cutting the electrode by using a manual punching machine to obtain the silicon negative electrode slice with the diameter of 12 mm.
The prepared silicon cathode electrode plate is transferred into a super-purification glove box filled with argon gas to assemble a 2032 type button half-cell for testing, a metal lithium foil is used as a counter electrode, and a diaphragm is a polypropylene microporous diaphragm. And (3) standing the packaged button type half cell for 6 hours, and then carrying out constant current charge-discharge cycle test in a voltage range of 0.01-1.5V.
Comparative example 2
Preparing a lithium ion battery silicon-carbon negative electrode by using a polyacrylic acid adhesive (the theoretical specific capacity is 500 mAh/g):
mixing the following components in percentage by weight of 80: 10: 10, mixing the silicon carbon material, Super-P conductive carbon black and polyacrylic acid (PAA) aqueous solution, and performing ball milling in a planetary ball mill for 1h to fully mix the materials to obtain uniformly dispersed negative electrode slurry; and coating the slurry on a copper foil current collector by using an automatic film coating agent, wherein the coating thickness is 50 mu m, and drying the copper foil current collector for 2h at 100 ℃ in vacuum to obtain the final electrode. And cutting the electrode by using a manual punching machine to obtain the silicon-carbon negative electrode plate with the diameter of 12 mm.
The prepared silicon-carbon cathode electrode piece is transferred into a super-purification glove box filled with argon gas to assemble a 2032 type button half cell for testing, metal lithium foil is used as a counter electrode, and a diaphragm is a polypropylene microporous diaphragm. And (3) standing the packaged button type half cell for 6 hours, and then carrying out constant current charge-discharge cycle test in a voltage range of 0.01-2.0V.
Example 1
Dissolving F127 and an acrylic monomer in deionized water, respectively preparing aqueous solutions with the mass fractions of 5% and 30%, adding lithium hydroxide powder to adjust the pH value of the acrylic aqueous solution to 5, and adding an ammonium persulfate initiator with the mass of 0.1 wt% of the acrylic monomer into the acrylic aqueous solution; heating the acrylic acid solution containing the initiator to 80 ℃, dropwise adding the F127 aqueous solution, reacting under the protection of nitrogen and magnetic stirring, keeping the reaction temperature at 80 ℃, and finishing the reaction after the reaction is carried out for 1 hour. Wherein the mass ratio of the acrylic monomer to the F127 is 9: 1. Thus, adhesive a1 was prepared.
The nano-silicon negative electrode of the lithium ion battery was prepared using the synthesized binder a1, and all the steps were the same as in comparative example 1, except that the binder used in the slurry preparation was the synthesized binder a 1.
The nano silicon negative assembled lithium ion battery prepared by using the network structure ion conductive adhesive A1 was tested, and all the procedures were the same as in comparative example 1.
Example 2
An ion-conductive polyacrylic acid-pluronic binder a1 having a network structure was synthesized in the same manner as in example 1.
The synthesized network structure ion conductive adhesive A1 was used to prepare a nano silicon carbon cathode of a lithium ion battery, and all the steps were the same as in comparative example 2, except that the adhesive used in the preparation of the slurry was synthesized adhesive A1.
The silicon-carbon negative electrode fabricated using the network-structured ion conductive binder a1 was assembled into a lithium ion battery and tested, all the procedures being the same as in comparative example 2.
As can be seen from fig. 2, when the adhesive is used in a lithium ion battery, electrode sheets before and after the cycle can show that the electrode sheets still maintain good integrity after 100 cycles of the cycle, and the adhesive can be visually shown to have good electrochemical properties when used in a lithium ion battery.
Example 3
The specific preparation method of the network-structured ion-conductive polyacrylic acid-pluronic adhesive in this example is the same as that of example 1, except that the pH of the acrylic acid aqueous solution was 6, the reaction temperature was 60 ℃, and the reaction time was 2 hours, thereby preparing an adhesive a 2.
The Sn-C cathode of the lithium ion battery is prepared by using the synthesized network structure ion conductive adhesive A2, and all the steps are the same as the comparative example 1, except that the adhesive used for preparing the slurry is the synthesized adhesive A2, the cathode material is Sn-C material, the electrode drying temperature is 80 ℃, and the drying time is 4 hours.
The Sn-C negative electrode assembled lithium ion battery prepared using the network-structured ion conductive binder a2 was tested, and all the procedures were the same as in comparative example 1.
Example 4
An ion-conductive polyacrylic acid-pluronic binder a2 having a network structure was synthesized in the same manner as in example 3.
The silicon-carbon cathode of the lithium ion battery is prepared by using the synthesized network structure ion conductive adhesive A2, and all the steps are the same as the comparative example 2, except that the adhesive used for preparing the slurry is the synthesized adhesive A2, the electrode drying temperature is 120 ℃, and the drying time is 10 h.
The silicon-carbon negative electrode fabricated using the network-structured ion conductive binder a2 was assembled into a lithium ion battery and tested, all the procedures being the same as in comparative example 2.
Example 5
The specific preparation method of the network-structured ion-conductive polyacrylic acid-pluronic adhesive in this example is the same as that of example 1, except that the pH of the acrylic acid aqueous solution was 7, the reaction temperature was 90 ℃, and the reaction time was 5 hours, thereby preparing an adhesive a 3.
The lithium ion battery graphite cathode is prepared by using the synthesized network structure ion conductive adhesive A3, and all the steps are the same as the comparative example 1, except that the adhesive used for preparing the slurry is the synthesized adhesive A3, the conductive additive is carbon nano tubes, and the electrode drying temperature is 80 ℃.
The graphite negative electrode fabricated using the network-structured ion conductive binder a3 was assembled into a lithium ion battery and tested, all the procedures being the same as in comparative example 2.
Example 6
An ion-conductive polyacrylic acid-pluronic binder a3 having a network structure was synthesized in the same manner as in example 5.
Mixing the phosphorus-carbon nanotube composite material, the carbon nanotubes and the prepared adhesive A3 according to the mass ratio of 70:15:15, uniformly mixing, and performing ball milling for 1h to prepare uniform cathode slurry; the method for preparing the battery by using the negative electrode slurry is the same as that of the example 1, but pure sodium is selected as a counter electrode, the electrolyte is an organic solution prepared by Ethylene Carbonate (EC) and diethyl carbonate (DEC) in a volume ratio of 1:1, and 1mol of sodium perchlorate (NaClO) is added into the organic solvent4) Furthermore, 10 vol% of fluoroethylene carbonate (FEC) was added as an additive to the electrolyte,the electrolyte is used as the electrolyte of the sodium ion battery. And (3) standing the battery assembled in the step for 4 hours, and then carrying out constant current (720mA/g) charge-discharge circulation on the battery by using a blue battery testing system between 0.01V and 2V.
Example 7
An ion-conductive polyacrylic acid-pluronic binder a3 having a network structure was synthesized in the same manner as in example 5.
The silicon-carbon cathode of the lithium ion battery is prepared by using the synthesized network structure ion conductive adhesive A3, and all the steps are the same as the comparative example 1, except that the adhesive used for preparing the slurry is the synthesized adhesive A3, and the conductive additive is the carbon nano tube.
The silicon-carbon negative electrode fabricated using the network-structured ion conductive binder a3 was assembled into a lithium ion battery and tested, all the procedures being the same as in comparative example 1.
Example 8
An ion-conductive polyacrylic acid-pluronic binder a3 having a network structure was synthesized in the same manner as in example 5.
The lithium ion battery nano silicon negative electrode is prepared by using the synthesized network structure ion conductive adhesive A3, and all the steps are the same as the comparative example 1, except that the adhesive used for preparing the slurry is the synthesized adhesive A3, and the conductive additive is carbon fiber.
The nano silicon negative assembled lithium ion battery prepared by using the network structure ion conductive adhesive A3 was tested, and all the procedures were the same as in comparative example 1.
Example 9
An ion-conductive polyacrylic acid-pluronic binder a3 having a network structure was synthesized in the same manner as in example 5.
The synthesized network structure ion conductive adhesive A3 is used for preparing the nano silicon cathode of the lithium ion battery, and all the steps are the same as the comparative example 1, except that the adhesive used for preparing the slurry is the synthesized adhesive A3, and the mass ratio of the nano silicon particles, the Super-P conductive carbon black and the adhesive A3 is 60:25: 15.
The nano silicon negative assembled lithium ion battery prepared by using the network structure ion conductive adhesive A3 was tested, and all the procedures were the same as in comparative example 1.
Example 10
An ion-conductive polyacrylic acid-pluronic binder a3 having a network structure was synthesized in the same manner as in example 5.
The nano silicon negative electrode of the lithium ion battery is prepared by using the synthesized network structure ion conductive adhesive A3, and all the steps are the same as the comparative example 1, except that the adhesive used in the slurry preparation is the synthesized adhesive A3, and the mass ratio of the nano silicon particles, the Super-P conductive carbon black and the adhesive A3 is 95:4.5: 0.5.
The nano silicon negative assembled lithium ion battery prepared by using the network structure ion conductive adhesive A3 was tested, and all the procedures were the same as in comparative example 1.
Example 11
The specific preparation method of the network-structured ion-conductive polyacrylic acid-pluronic adhesive in this example was the same as that of example 1, except that the pH of the aqueous acrylic acid solution was 7 and the amount of the initiator was 0.05% by mass of the acrylic acid monomer, thereby preparing an adhesive a 4.
The synthesized network structure ion conductive adhesive A4 was used to prepare a nano-silicon negative electrode of a lithium ion battery, and all the steps were the same as in comparative example 1, except that the adhesive used in the preparation of the slurry was synthesized adhesive A4.
The nano silicon negative assembled lithium ion battery prepared by using the network structure ion conductive adhesive A4 was tested, and all the procedures were the same as in comparative example 1.
Example 12
An ion-conductive polyacrylic acid-pluronic adhesive a4 having a network structure was synthesized in the same manner as in example 11.
The synthesized network structure ion conductive binder a4 was used to prepare a silicon carbon negative electrode of a lithium ion battery, all the steps were the same as in comparative example 2, except that the binder used in the slurry preparation was the synthesized binder a 4.
The silicon-carbon negative electrode fabricated using the network-structured ion conductive binder a4 was assembled into a lithium ion battery and tested, all the procedures being the same as in comparative example 2.
As can be seen from FIG. 1, the electrode sheet prepared by the adhesive has a high average peel strength of 30N/m.
Example 13
The specific preparation method of the network-structured ion-conductive polyacrylic acid-pluronic binder in this example was the same as that of example 1, except that the pH of the aqueous acrylic acid solution was 6 and the initiator was sodium metabisulfite, thereby preparing binder a 5.
The synthesized network structure ion conductive adhesive A5 was used to prepare a nano-silicon negative electrode of a lithium ion battery, and all the steps were the same as in comparative example 1, except that the adhesive used in the preparation of the slurry was synthesized adhesive A5.
The nano silicon negative assembled lithium ion battery prepared by using the network structure ion conductive adhesive A5 was tested, and all the procedures were the same as in comparative example 1.
Example 14
The specific preparation method of the network-structured ion-conductive polyacrylic acid-pluronic adhesive in this example was the same as that of example 1, except that the pH of the aqueous acrylic acid solution was 6 and the mass ratio of the acrylic acid monomer to F127 was 8:2, thereby preparing an adhesive a 6.
The synthesized network structure ion conductive adhesive A6 was used to prepare a nano-silicon negative electrode of a lithium ion battery, and all the steps were the same as in comparative example 1, except that the adhesive used in the preparation of the slurry was synthesized adhesive A6.
The nano silicon negative assembled lithium ion battery prepared by using the network structure ion conductive adhesive A6 was tested, and all the procedures were the same as in comparative example 1.
Example 15
The specific preparation method of the network-structured ion-conductive polyacrylic acid-pluronic adhesive in this example was the same as that of example 1, except that the pH of the aqueous acrylic acid solution was 6 and the mass ratio of the acrylic acid monomer to F127 was 7:3, thereby preparing an adhesive a 7.
The synthesized network structure ion conductive adhesive A7 is used for preparing the nano silicon cathode of the lithium ion battery, and all the steps are the same as the comparative example 1, except that the adhesive used for preparing the slurry is the synthesized adhesive A7, and the mass ratio of the nano silicon particles, the Super-P conductive carbon black and the adhesive A3 is 95:20: 10.
The nano silicon negative assembled lithium ion battery prepared by using the network structure ion conductive adhesive A7 was tested, and all the procedures were the same as in comparative example 1.
Example 16
The specific preparation method of the network-structured ionic conductive polyacrylic acid-pluronic adhesive in this example is the same as that of example 1, except that the mass fraction of the acrylic acid aqueous solution is 25%, and the amount of the initiator is 2% of the mass of the acrylic acid monomer, thereby preparing an adhesive A8.
The nano silicon negative electrode of the lithium ion battery is prepared by using the synthesized network structure ion conductive adhesive A8, and all the steps are the same as the comparative example 1, except that the adhesive used in the slurry preparation is the synthesized adhesive A8, and the mass ratio of the nano silicon particles, the Super-P conductive carbon black and the adhesive A3 is 60:4.5: 0.5.
The nano silicon negative assembled lithium ion battery prepared by using the network structure ion conductive adhesive A8 was tested, and all the procedures were the same as in comparative example 1.
Example 17
The specific preparation method of the network-structured ion-conductive polyacrylic acid-pluronic adhesive in this example is the same as that of example 1, except that the mass fraction of the acrylic acid aqueous solution is 50%, thereby preparing an adhesive a 9.
The synthesized network structure ion conductive adhesive A9 is used for preparing the nano silicon cathode of the lithium ion battery, and all the steps are the same as the comparative example 1, except that the adhesive used for preparing the slurry is the synthesized adhesive A9, and the mass ratio of the nano silicon particles, the Super-P conductive carbon black and the adhesive A3 is 95:25: 15.
The nano silicon negative assembled lithium ion battery prepared by using the network structure ion conductive adhesive A9 was tested, and all the procedures were the same as in comparative example 1.
Example 18
The specific preparation method of the network-structured ion-conductive polyacrylic acid-pluronic adhesive in this example is the same as that in example 1, except that the mass fraction of the pluronic aqueous solution is 10%, thereby preparing an adhesive a 10.
The synthesized network structure ion conductive adhesive A10 is used for preparing the nano silicon cathode of the lithium ion battery, and all the steps are the same as the comparative example 1, except that the adhesive used for preparing the slurry is the synthesized adhesive A10, and the mass ratio of the nano silicon particles, the Super-P conductive carbon black and the adhesive A3 is 60:5: 8.
The nano silicon negative assembled lithium ion battery prepared by using the network structure ion conductive adhesive A10 was tested, and all the procedures were the same as in comparative example 1.
Example 19
The specific preparation method of the network-structured ion-conductive polyacrylic acid-pluronic adhesive in this example is the same as that in example 1, except that the mass fraction of the pluronic aqueous solution is 30%, thereby preparing an adhesive a 11.
The synthesized network structure ion conductive adhesive A11 is used for preparing the nano silicon cathode of the lithium ion battery, and all the steps are the same as the comparative example 1, except that the adhesive used for preparing the slurry is the synthesized adhesive A11, and the mass ratio of the nano silicon particles, the Super-P conductive carbon black and the adhesive A3 is 70:4.5: 12.
The synthesized network structure ion conductive adhesive A11 was used to prepare a nano-silicon negative electrode of a lithium ion battery, and all the steps were the same as in comparative example 1, except that the adhesive used in the preparation of the slurry was synthesized adhesive A11.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. The preparation method of the network structure ionic conductive adhesive is characterized by comprising the following steps:
step 1: dissolving pluronic in deionized water to prepare a pluronic water solution; dissolving an acrylic acid monomer in deionized water to prepare an acrylic acid aqueous solution, and adding lithium hydroxide powder to adjust the pH value of the acrylic acid aqueous solution;
step 2: adding an initiator into the acrylic acid aqueous solution with the pH value adjusted, heating the acrylic acid aqueous solution to 60-90 ℃, and adding the pluronic aqueous solution prepared in the step 1;
and step 3: and (3) magnetically stirring the reaction solution obtained in the step (2), reacting under the protection of nitrogen, and finishing the reaction after reacting for 1-5h to obtain the network structure ion conductive adhesive formed by crosslinking polyacrylic acid and pluronic.
2. The method for preparing the network structure ionic conduction adhesive according to claim 1, wherein the segment of the pluronic is polyoxyethylene polyoxypropylene ether.
3. The method for preparing the network structure ionic conduction adhesive according to claim 1, wherein in the step 1, the mass concentration of the pluronic aqueous solution is 5% -30%;
in the step 2, the mass concentration of the acrylic acid aqueous solution is 25-50%, and lithium hydroxide powder is added to adjust the pH value of the acrylic acid aqueous solution to 5-7.
4. The method for preparing the network structure ion conductive adhesive according to claim 1, wherein the initiator is any one of ammonium persulfate and sodium metabisulfite, and the amount of the initiator is 0.05-2% of the mass of the acrylic monomer.
5. The method for preparing the network structure ionic conduction adhesive according to claim 1, wherein the mass ratio of the acrylic monomer to the pluronic is (7-9) to (1-3).
6. A network structure ion-conductive adhesive, which is prepared by the method for preparing the network structure ion-conductive adhesive according to any one of claims 1 to 5.
7. The application of the network structure ion conductive adhesive in the preparation of the secondary battery negative electrode is characterized in that a negative electrode active material and a conductive additive are dispersed in a network structure ion conductive adhesive aqueous solution, the mixture is subjected to ball milling to obtain a uniformly mixed slurry, the slurry is uniformly coated on a copper foil current collector, and the secondary battery negative electrode is obtained after vacuum drying.
8. The use of claim 7, wherein the mass concentration of the aqueous solution of the network structure ion conductive adhesive is 5%, and the absolute dry mass ratio of the negative electrode active material, the conductive additive and the network structure ion conductive adhesive is (60-95): (4.5-25): (0.5-15).
9. The application of claim 7, wherein the negative active material is selected from carbon-based materials and composites thereof, silicon-based materials and composites thereof, and phosphorus-based materials and composites thereof; the conductive additive is a composite conductive additive formed by mixing carbon black, carbon nano tubes, carbon fibers or two of the carbon black, the carbon nano tubes and the carbon fibers.
10. Use according to claim 7, wherein the temperature of the vacuum drying is 80-120 ℃ and the drying time is 2-10 h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110304080.XA CN113113605B (en) | 2021-03-22 | 2021-03-22 | Network structure ion conductive adhesive and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110304080.XA CN113113605B (en) | 2021-03-22 | 2021-03-22 | Network structure ion conductive adhesive and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113113605A true CN113113605A (en) | 2021-07-13 |
| CN113113605B CN113113605B (en) | 2022-08-09 |
Family
ID=76712087
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110304080.XA Active CN113113605B (en) | 2021-03-22 | 2021-03-22 | Network structure ion conductive adhesive and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113113605B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113964294A (en) * | 2021-10-28 | 2022-01-21 | 西安交通大学 | Lithium ion battery cathode and preparation method and application thereof |
| CN114122398A (en) * | 2021-10-29 | 2022-03-01 | 西安交通大学 | Integrated conductive adhesive and preparation method and application thereof |
| CN114122399A (en) * | 2021-10-29 | 2022-03-01 | 西安交通大学 | Battery silicon-carbon cathode composite adhesive and preparation method and application thereof |
| CN114573746A (en) * | 2021-12-31 | 2022-06-03 | 瑞红锂电池材料(苏州)有限公司 | High-lithium-content high-molecular-weight lithium acrylate emulsion and preparation method and application thereof |
| CN114976002A (en) * | 2022-04-28 | 2022-08-30 | 清华大学山西清洁能源研究院 | Adhesive, preparation method thereof, lithium-sulfur battery positive electrode and lithium-sulfur battery |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20120071448A (en) * | 2010-12-23 | 2012-07-03 | 한국기초과학지원연구원 | Lithium titanium oxide electrode material having carbon for lithium secondary batteries |
| CN105131182A (en) * | 2015-09-06 | 2015-12-09 | 山东大学 | Pluronic-poly(beta-amino ester) polymer and synthesis and application methods |
| CN106058208A (en) * | 2016-07-29 | 2016-10-26 | 天津巴莫科技股份有限公司 | Sulfur-carbon positive pole material for lithium-sulfur secondary battery and preparation method of sulfur-carbon positive pole material |
| CN109888286A (en) * | 2019-01-23 | 2019-06-14 | 西安交通大学 | A kind of poly acrylic acid-poly ethylene glycol hydrogel adhesive and its preparation method and application of Dynamic ion crosslinking |
| CN110858522A (en) * | 2018-08-26 | 2020-03-03 | 天津大学 | Reversible overheating self-protection water system electrolyte based on poloxamer-polyacrylic acid graft copolymer, preparation method and application |
| CN111009647A (en) * | 2019-12-10 | 2020-04-14 | 中南大学 | Lithium borosilicate alloy cathode active material of lithium secondary battery, cathode, preparation and application thereof |
| CN111261874A (en) * | 2020-02-12 | 2020-06-09 | 西安交通大学 | Lithium ion battery cathode and preparation method and application thereof |
-
2021
- 2021-03-22 CN CN202110304080.XA patent/CN113113605B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20120071448A (en) * | 2010-12-23 | 2012-07-03 | 한국기초과학지원연구원 | Lithium titanium oxide electrode material having carbon for lithium secondary batteries |
| CN105131182A (en) * | 2015-09-06 | 2015-12-09 | 山东大学 | Pluronic-poly(beta-amino ester) polymer and synthesis and application methods |
| CN106058208A (en) * | 2016-07-29 | 2016-10-26 | 天津巴莫科技股份有限公司 | Sulfur-carbon positive pole material for lithium-sulfur secondary battery and preparation method of sulfur-carbon positive pole material |
| CN110858522A (en) * | 2018-08-26 | 2020-03-03 | 天津大学 | Reversible overheating self-protection water system electrolyte based on poloxamer-polyacrylic acid graft copolymer, preparation method and application |
| CN109888286A (en) * | 2019-01-23 | 2019-06-14 | 西安交通大学 | A kind of poly acrylic acid-poly ethylene glycol hydrogel adhesive and its preparation method and application of Dynamic ion crosslinking |
| CN111009647A (en) * | 2019-12-10 | 2020-04-14 | 中南大学 | Lithium borosilicate alloy cathode active material of lithium secondary battery, cathode, preparation and application thereof |
| CN111261874A (en) * | 2020-02-12 | 2020-06-09 | 西安交通大学 | Lithium ion battery cathode and preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| MOHAMMED LEADI COLE 等: "Preparation of Stable Multiple W/O/W Emulsions Using Pluronic (Poloxamer)：Poly(acrylic Acid) Complexes", 《JOURNAL OF COLLIDE AND INTERFACE SCIENCE》 * |
| 马文狄: "泊洛沙姆-聚丙烯酸接枝共聚物原位凝胶的研究", 《万方学位论文数据库》 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113964294A (en) * | 2021-10-28 | 2022-01-21 | 西安交通大学 | Lithium ion battery cathode and preparation method and application thereof |
| CN113964294B (en) * | 2021-10-28 | 2024-04-12 | 西安交通大学 | Lithium ion battery negative electrode and preparation method and application thereof |
| CN114122398A (en) * | 2021-10-29 | 2022-03-01 | 西安交通大学 | Integrated conductive adhesive and preparation method and application thereof |
| CN114122399A (en) * | 2021-10-29 | 2022-03-01 | 西安交通大学 | Battery silicon-carbon cathode composite adhesive and preparation method and application thereof |
| CN114122399B (en) * | 2021-10-29 | 2023-08-25 | 西安交通大学 | Silicon-carbon negative electrode composite adhesive for battery, and preparation method and application thereof |
| CN114122398B (en) * | 2021-10-29 | 2023-12-19 | 西安交通大学 | Integrated conductive adhesive and preparation method and application thereof |
| CN114573746A (en) * | 2021-12-31 | 2022-06-03 | 瑞红锂电池材料(苏州)有限公司 | High-lithium-content high-molecular-weight lithium acrylate emulsion and preparation method and application thereof |
| CN114573746B (en) * | 2021-12-31 | 2023-08-18 | 瑞红锂电池材料(苏州)有限公司 | High-lithium-content high-molecular-weight lithium acrylate emulsion and preparation method and application thereof |
| CN114976002A (en) * | 2022-04-28 | 2022-08-30 | 清华大学山西清洁能源研究院 | Adhesive, preparation method thereof, lithium-sulfur battery positive electrode and lithium-sulfur battery |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113113605B (en) | 2022-08-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113113605B (en) | Network structure ion conductive adhesive and preparation method and application thereof | |
| CN111261874B (en) | Lithium ion battery cathode and preparation method and application thereof | |
| CN109004220B (en) | Boric acid compound modified lithium ion battery silicon cathode and preparation method thereof | |
| CN109888170B (en) | Three-dimensional network adhesive for secondary battery, preparation method of three-dimensional network adhesive, negative electrode slurry and negative electrode material | |
| KR102260940B1 (en) | Dispersant of conductive carbon material for lithium ion battery, slurry for electrode of lithium ion battery, electrode for lithium ion battery and lithium ion battery | |
| CN109888286B (en) | Dynamic ion crosslinked polyacrylic acid-polyethylene glycol hydrogel adhesive and preparation method and application thereof | |
| CN111326789A (en) | Semi-interpenetrating network flame-retardant solid lithium ion electrolyte, solid lithium battery and preparation method | |
| CN108400335B (en) | Binder, composition, electrode material and preparation method thereof | |
| CN1222063C (en) | Lithium ion cell, electrode of lithium ion cell and its preparation method | |
| CN110190284B (en) | Water-based binder for lithium-sulfur battery positive electrode and preparation method and application thereof | |
| CN113659145A (en) | Cathode slurry and preparation method thereof, and lithium ion battery and preparation method thereof | |
| CN111171185A (en) | Preparation and use method of cyclodextrin series connection polyaniline prepolymer as binder | |
| CN109802107B (en) | Preparation method of polyalkenyl composite negative electrode material for sodium ion battery | |
| CN107706393B (en) | High-capacity solid lithium ion battery and preparation method thereof | |
| CN110492101B (en) | Lithium ion battery cathode binder and preparation method and application thereof | |
| CN113471512A (en) | Low-temperature lithium battery | |
| CN110993953B (en) | Positive plate, solid-state chemical power supply and preparation method | |
| CN112310399A (en) | Lithium ion battery silicon negative electrode binder and electrode preparation method and application thereof | |
| CN112164769A (en) | Preparation method of silicon-based negative electrode material based on polyimide-based electrode binder | |
| CN114725313B (en) | Silicon-based negative plate and preparation method and application thereof | |
| CN116014079A (en) | Lignin water-based composite battery binder and preparation method and application of silicon-based negative plate thereof | |
| CN114464880B (en) | Self-repairing composite solid lithium ion battery electrolyte and preparation method thereof | |
| CN116111091A (en) | Adhesive composition, sodium ion battery positive electrode slurry and sodium ion battery | |
| CN109659475A (en) | A kind of preparation method of high-performance high-voltage lithium ion battery | |
| CN115172680A (en) | High-capacity high-rate lithium ion battery and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |