CN111554933A - Functional nano conductor slurry, preparation method thereof and lithium battery - Google Patents
Functional nano conductor slurry, preparation method thereof and lithium battery Download PDFInfo
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- CN111554933A CN111554933A CN202010398197.4A CN202010398197A CN111554933A CN 111554933 A CN111554933 A CN 111554933A CN 202010398197 A CN202010398197 A CN 202010398197A CN 111554933 A CN111554933 A CN 111554933A
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Abstract
The invention relates to functional nano conductor slurry, a preparation method thereof and a lithium battery, wherein the functional nano conductor slurry comprises the following components in parts by weight: 20 wt% -99.95 wt% of solvent and 0.05 wt% -80 wt% of solute; wherein the solute comprises 0.05 wt% -79.98 wt% of functional powder material, 0 wt% -79.95 wt% of oxide powder material, 0 wt% -2 wt% of anti-settling agent, 0 wt% -20 wt% of binder, 0 wt% -20 wt% of dispersing agent, 0 wt% -5 wt% of conductive agent and 0 wt% -2 wt% of auxiliary agent; the functional powder material comprises a lithium-containing crystal material, wherein lithium ions occupy one or more combinations of tetrahedral sites, octahedral sites or hexadecahedral sites of the crystal structure; in the functional powder material, the lithium ion conductivity is more than or equal to 10‑6S·cm‑1An order of magnitude; functional nano conductor slurry used for diaphragm coating material, anode material coating material, cathode material coating material and anode materialAny one of a material additive, an anode material additive, or a solid electrolyte additive.
Description
Technical Field
The invention relates to the technical field of lithium battery materials, in particular to functional nano conductor slurry, a preparation method thereof and a lithium battery.
Background
At present, lithium ion secondary batteries are widely used in portable electric appliances such as mobile phones and notebook computers. With the development of the technology, the lithium ion battery has a good application prospect in the fields of electric automobiles and energy storage, and will certainly have a profound influence on the life of people in the future.
With the wide application and rapid development of lithium batteries, people have higher and higher performance requirements on lithium ion batteries, and the lithium batteries are required to have higher capacity, better capacity retention rate in repeated charge and discharge processes, good cycle performance and longer service life.
The pulping process has an influence on the quality of the product in the whole production process of the lithium ion battery of more than 40 percent, and is the most important link in the whole production process. However, most of the prior art still adopts the traditional slurry preparation process, and adopts the high-speed dispersion process to disperse the slurry, and the slurry prepared by the process is easy to agglomerate, and has the defects of poor uniformity, poor stability, long preparation process time and the like. The lithium ion battery prepared by the slurry has the problem of poor consistency in performance, so that the matching and the use of the lithium ion battery are influenced.
Therefore, there is an urgent need for a novel slurry and a preparation method thereof to make up for the drawbacks of the prior art.
Disclosure of Invention
The embodiment of the invention provides functional nano conductor slurry, a preparation method thereof and a lithium battery, which are used for solving the problems in the prior art, and the performance of the functional nano conductor slurry is improved by optimizing the component composition of the nano conductor slurry and improving the quality of a pulping process.
In a first aspect, an embodiment of the present invention provides a functional nano conductor paste, including, in parts by mass: 20 wt% -99.95 wt% of solvent and 0.05 wt% -80 wt% of solute;
wherein the solute comprises 0.05 wt% -79.98 wt% of functional powder material, 0 wt% -79.95 wt% of oxide powder material, 0 wt% -2 wt% of anti-settling agent, 0 wt% -20 wt% of binder, 0 wt% -20 wt% of dispersing agent, 0 wt% -5 wt% of conductive agent and 0 wt% -2 wt% of auxiliary agent;
the functional powder material comprises a lithium-containing crystal material, wherein lithium ions occupy one or more combinations of tetrahedral sites, octahedral sites or hexadecahedral sites of the crystal structure; in the functional powder material, the lithium ion conductivity is more than or equal to 10-6S·cm-1An order of magnitude;
the functional nano conductor slurry is used for any one of a diaphragm coating material, a positive electrode material coating material, a negative electrode material coating material, a positive electrode material additive, a negative electrode material additive or a solid electrolyte additive.
Preferably, the lithium element-containing crystal material further contains titanium element; wherein in the titanium element, the mass ratio of tetravalent titanium accounts for 3-30%.
Preferably, the lithium element-containing crystal material specifically includes: one or more of lithium lanthanum zirconium oxide, lithium lanthanum niobium oxide, lithium lanthanum tantalum oxide, lithium titanium silicate, lithium titanium aluminum phosphate, lithium lanthanum titanium oxide, lithium aluminum titanium oxide, zirconium lithium phosphate, lithium zinc phosphate, lithium calcium titanium oxide and zirconium lithium silicate.
Preferably, the oxide powder material includes: one or more of aluminum oxide, boron oxide, silicon oxide, phosphorus pentoxide, magnesium oxide, zirconium oxide, calcium oxide, sodium oxide and potassium oxide; the particle size of the oxide powder material is between 1nm and 100 um;
the anti-settling agent comprises: one or more of polyamide wax, polyoxyethylene fatty amine alcohol, polyoxyethylene fatty alcohol sulfate, nano-cellulose, polyglycol ether or titanate coupling agent;
the adhesive comprises: one or more of polyvinylidene fluoride, polyvinylidene fluoride-hexafluoropropylene copolymer, carboxymethyl cellulose, sodium carboxymethyl cellulose, polymethyl methacrylate, polyacrylonitrile, styrene butadiene rubber, polyvinyl alcohol, polytetrafluoroethylene, polyolefins, fluorinated rubber, sodium alginate, polyacrylamide, polymethyl methacrylate-butyl acrylate, ethylene-vinyl acetate copolymer, polyvinyl acetate or polyurethane or gelatin;
the dispersant comprises: one or more of sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, sodium dodecyl phosphate, sodium hexametaphosphate, polyacrylic acid, polybutyl acrylate-styrene-acrylic acid, hexadecyl trimethyl ammonium bromide, polyethylene glycol, polyvinylpyrrolidone, polyacrylate, polymethacrylate, maleic anhydride-styrene copolymer, octyl phenol polyoxyethylene ether, monoglyceride, glyceryl tristearate, oleic acid acyl, sodium linoleate, tannic acid, sodium pyrophosphate or succinic acid;
the conductive agent includes: one or more of a graphite conductive agent, conductive carbon black, graphene or metal powder; the graphite conductive agent includes: one or more of KS-6, KS-15, SFG-6 and SFG-15; the conductive carbon black comprises: one or more of acetylene black, Super P, Super S, 350G, carbon fiber VGCF, carbon nanotube CNTs, Ketjen black and activated carbon; the metal powder includes: one or more of zinc powder, copper powder, aluminum powder, silver powder, gold powder, tungsten powder and tin powder;
the auxiliary agent comprises: one or more of polydimethylsiloxane, isophorone, diacetone alcohol, Solvesso150, silicone oil, polyethers, sodium alkyl polyoxyethylene ether carboxylate, polyoxyethylene ether, polyoxyethylene alkylphenol ether, sodium alkyl benzene sulfonate, alkylphenol polyoxyethylene ether, polyoxyethylene alkylamine, sodium lauryl sulfate or polyoxyethylene amide.
Preferably, the solvent comprises: one or more of deionized water, alcohol, N-methyl pyrrolidone, tetrahydrofuran, dimethylformamide, isopropanol, ethyl acetate or acetone.
In a second aspect, an embodiment of the present invention provides a method for preparing the functional nano-conductor paste according to the first aspect, where the method for preparing the functional nano-conductor paste comprises:
adding 0 wt% -20 wt% of binder, 0 wt% -2 wt% of anti-settling agent and solvent of the functional nano conductor slurry into a pre-stirring tank according to the required proportion by the total mass part of solute in the required functional nano conductor slurry, and dispersing for 0.5-1.5 hours at the dispersion speed of 1000-5000 rpm to obtain uniformly dispersed slurry; wherein the solvent accounts for 20-99.95 wt% of the total mass of the functional nano conductor slurry; the solute accounts for 0.05 to 80 weight percent of the total mass of the functional nano conductor slurry.
Carrying out ultrasonic treatment on the slurry for 0.5-1.0 h at an ultrasonic frequency of 1-10 kHz to obtain first slurry;
adding 0.05-79.98 wt% of functional powder material, 0-79.95 wt% of oxide powder material and 0-20 wt% of dispersing agent into the first slurry according to the required proportion, dispersing for 0.5-1.5 hours at the dispersion speed of 1000-5000 rpm, adding a centrifuge for centrifugation for 0.5-1.0 hour, and adding the centrifuged upper slurry into a sand mill for sand milling for 0.5-1.5 hours; the functional powder material comprises a lithium-containing crystal material, wherein lithium ions occupy one or more combinations of tetrahedral sites, octahedral sites or hexadecahedral sites of the crystal structure; in the functional powder material, the lithium ion conductivity is more than or equal to 10-6S·cm-1An order of magnitude;
taking out the materials by sanding, adding 0-5 wt% of conductive agent and 0-2 wt% of auxiliary agent, stirring and dispersing to obtain second slurry; wherein the stirring speed is 10rpm-50rpm, and the dispersing speed is 1000rpm-5000 rpm;
and carrying out ultrasonic treatment on the second slurry for 0.5-1.0 hour at the ultrasonic frequency of 1-10 kHz to obtain the required functional nano conductor slurry.
Preferably, the particle size of the functional powder material and the particle size of the oxide powder material are both between 1nm and 100 um.
Preferably, the lithium element-containing crystal material further contains a tetravalent titanium element; the mass ratio of tetravalent titanium element content in the functional powder material is 3-30%.
Preferably, the lithium element-containing crystal material specifically includes: one or more of lithium lanthanum zirconium oxide, lithium lanthanum niobium oxide, lithium lanthanum tantalum oxide, lithium titanium silicate, lithium titanium aluminum phosphate, lithium lanthanum titanium oxide, lithium aluminum titanium oxide, zirconium lithium phosphate, lithium zinc phosphate, lithium calcium titanium oxide and zirconium lithium silicate;
the oxide powder material comprises: one or more of aluminum oxide, boron oxide, silicon oxide, phosphorus pentoxide, magnesium oxide, zirconium oxide, calcium oxide, sodium oxide and potassium oxide; the particle size of the oxide powder material is between 1nm and 100 um;
the anti-settling agent comprises: one or more of polyamide wax, polyoxyethylene fatty amine alcohol, polyoxyethylene fatty alcohol sulfate, nano-cellulose, polyglycol ether or titanate coupling agent;
the adhesive comprises: one or more of polyvinylidene fluoride, polyvinylidene fluoride-hexafluoropropylene copolymer, carboxymethyl cellulose, sodium carboxymethyl cellulose, polymethyl methacrylate, polyacrylonitrile, styrene butadiene rubber, polyvinyl alcohol, polytetrafluoroethylene, polyolefins, fluorinated rubber, sodium alginate, polyacrylamide, polymethyl methacrylate-butyl acrylate, ethylene-vinyl acetate copolymer, polyvinyl acetate or polyurethane or gelatin;
the dispersant comprises: one or more of sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, sodium dodecyl phosphate, sodium hexametaphosphate, polyacrylic acid, polybutyl acrylate-styrene-acrylic acid, hexadecyl trimethyl ammonium bromide, polyethylene glycol, polyvinylpyrrolidone, polyacrylate, polymethacrylate, maleic anhydride-styrene copolymer, octyl phenol polyoxyethylene ether, monoglyceride, glyceryl tristearate, oleic acid acyl, sodium linoleate, tannic acid, sodium pyrophosphate or succinic acid;
the conductive agent includes: one or more of a graphite conductive agent, conductive carbon black, graphene or metal powder; the graphite conductive agent includes: one or more of KS-6, KS-15, SFG-6 and SFG-15; the conductive carbon black comprises: one or more of acetylene black, Super P, Super S, 350G, carbon fiber VGCF, carbon nanotube CNTs, Ketjen black and activated carbon; the metal powder includes: one or more of zinc powder, copper powder, aluminum powder, silver powder, gold powder, tungsten powder and tin powder;
the auxiliary agent comprises: one or more of polydimethylsiloxane, isophorone, diacetone alcohol, Solvesso150, silicone oil, polyethers, sodium alkyl polyoxyethylene ether carboxylate, polyoxyethylene ether, polyoxyethylene alkylphenol ether, sodium alkyl benzene sulfonate, alkylphenol polyoxyethylene ether, polyoxyethylene alkylamine, sodium lauryl sulfate or polyoxyethylene amide;
the solvent comprises: one or more of deionized water, alcohol, N-methyl pyrrolidone, tetrahydrofuran, dimethylformamide, isopropanol, ethyl acetate or acetone.
In a third aspect, embodiments of the present invention provide a lithium battery comprising the functional nanoconductor paste of any one of the preceding claims 1 to 5.
The functional nano conductor slurry provided by the invention improves the quality of the pulping process by optimizing the component composition of the nano conductor slurry, so that the performance of the functional nano conductor slurry is improved. The functional nano conductor slurry of the lithium element-containing crystal material can effectively reduce the internal resistance of the battery, and can improve the lithium ion content of the battery, thereby improving the conductivity. The functional nano conductor slurry provided by the invention has the characteristics of large specific surface area and high porosity, and is convenient for lithium ion conduction.
Drawings
The technical solutions of the embodiments of the present invention are further described in detail with reference to the accompanying drawings and embodiments.
Fig. 1 is a flow chart of a method for preparing a functional nano-conductor paste according to an embodiment of the present invention;
FIG. 2 is a charge-discharge curve of the slurry provided in example 1 of the present invention;
FIG. 3 is a graph comparing the half-cell cycle performance tests of example 2 of the present invention with the comparative example;
fig. 4 is a graph comparing the half-cell cycle performance tests of example 5 of the present invention and comparative example.
Detailed Description
The invention is further illustrated by the following figures and specific examples, but it should be understood that these examples are for the purpose of illustration only and are not to be construed as in any way limiting the present invention, i.e., as in no way limiting its scope.
The functional nano conductor slurry comprises the following components in parts by weight: 20 wt% -99.95 wt% of solvent and 0.05 wt% -80 wt% of solute;
wherein the solute comprises 0.05 wt% -79.98 wt% of functional powder material, 0 wt% -79.95 wt% of oxide powder material, 0 wt% -2 wt% of anti-settling agent, 0 wt% -20 wt% of binder, 0 wt% -20 wt% of dispersing agent, 0 wt% -5 wt% of conductive agent and 0 wt% -2 wt% of auxiliary agent;
the functional powder material comprises a lithium-containing crystal material, wherein lithium ions occupy one or more combinations of tetrahedral sites, octahedral sites or hexadecahedral sites of the crystal structure; in the functional powder material, the lithium ion conductivity is more than or equal to 10- 6S·cm-1An order of magnitude;
in an alternative, the lithium-containing crystal material may further include titanium; wherein, in the titanium element, the mass ratio of tetravalent titanium accounts for 3-30%. The introduction of tetravalent titanium contributes to the improvement of the ionic conductivity, and the stability of the material.
Specifically, the lithium element-containing crystal material may specifically include: one or more of lithium lanthanum zirconium oxide, lithium lanthanum niobium oxide, lithium lanthanum tantalum oxide, lithium titanium silicate, lithium titanium aluminum phosphate, lithium lanthanum titanium oxide, lithium aluminum titanium oxide, zirconium lithium phosphate, lithium zinc phosphate, lithium calcium titanium oxide and zirconium lithium silicate.
The oxide powder material comprises: one or more of aluminum oxide, boron oxide, silicon oxide, phosphorus pentoxide, magnesium oxide, zirconium oxide, calcium oxide, sodium oxide and potassium oxide; the particle size of the oxide powder material is between 1nm and 100 um;
the anti-settling agent comprises: one or more of polyamide wax, polyoxyethylene fatty amine alcohol, polyoxyethylene fatty alcohol sulfate, nano-cellulose, polyglycol ether or titanate coupling agent;
the adhesive comprises: one or more of polyvinylidene fluoride, polyvinylidene fluoride-hexafluoropropylene copolymer, carboxymethyl cellulose, sodium carboxymethyl cellulose, polymethyl methacrylate, polyacrylonitrile, styrene butadiene rubber, polyvinyl alcohol, polytetrafluoroethylene, polyolefins, fluorinated rubber, sodium alginate, polyacrylamide, polymethyl methacrylate-butyl acrylate, ethylene-vinyl acetate copolymer, polyvinyl acetate or polyurethane or gelatin;
the dispersant comprises: one or more of sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, sodium dodecyl phosphate, sodium hexametaphosphate, polyacrylic acid, polybutyl acrylate-styrene-acrylic acid, hexadecyl trimethyl ammonium bromide, polyethylene glycol, polyvinylpyrrolidone, polyacrylate, polymethacrylate, maleic anhydride-styrene copolymer, octyl phenol polyoxyethylene ether, monoglyceride, glyceryl tristearate, oleic acid acyl, sodium linoleate, tannic acid, sodium pyrophosphate or succinic acid;
the conductive agent includes: one or more of a graphite conductive agent, conductive carbon black, graphene or metal powder; the graphite conductive agent includes: one or more of KS-6, KS-15, SFG-6 and SFG-15; the conductive carbon black comprises: one or more of acetylene black, Super P, Super S, 350G, carbon fiber VGCF, carbon nanotube CNTs, Ketjen black and activated carbon; the metal powder includes: one or more of zinc powder, copper powder, aluminum powder, silver powder, gold powder, tungsten powder and tin powder;
the auxiliary agent comprises: one or more of polydimethylsiloxane, isophorone, diacetone alcohol, Solvesso150, silicone oil, polyethers, sodium alkyl polyoxyethylene ether carboxylate, polyoxyethylene ether, polyoxyethylene alkylphenol ether, sodium alkyl benzene sulfonate, alkylphenol polyoxyethylene ether, polyoxyethylene alkylamine, sodium lauryl sulfate or polyoxyethylene amide.
The solvent comprises: one or more of deionized water, alcohol, N-methyl pyrrolidone, tetrahydrofuran, dimethylformamide, isopropanol, ethyl acetate or acetone.
The functional nano conductor slurry provided by the embodiment is used for any one of a separator coating material, a positive electrode material coating material, a negative electrode material coating material, a positive electrode material additive, a negative electrode material additive or a solid electrolyte additive.
The preparation method of the functional nano conductor slurry disclosed by the invention is as shown in a method step flow shown in figure 1, and comprises the following steps:
wherein the solvent accounts for 20-99.95 wt% of the total mass of the functional nano conductor slurry; the solute accounts for 0.05 to 80 weight percent of the total mass of the functional nano conductor slurry.
specifically, the particle sizes of the added functional powder material and the added oxide powder material are both 1nm-100 um.
wherein the stirring speed is 10rpm-50rpm, and the dispersing speed is 1000rpm-5000 rpm;
and 150, carrying out ultrasonic treatment on the second slurry for 0.5-1.0 hour at the ultrasonic frequency of 1-10 kHz to obtain the required functional nano conductor slurry.
The materials mentioned in the above method steps have already been described previously and are not described herein again.
The functional nano conductor slurry prepared by the invention can be used for a diaphragm coating material, a positive electrode material coating material, a negative electrode material coating material, a positive electrode material additive, a negative electrode material additive or an additive of a compound solid electrolyte and the like.
The functional nano conductor slurry provided by the invention improves the quality of the pulping process by optimizing the component composition of the nano conductor slurry, so that the performance of the functional nano conductor slurry is improved. The functional nano conductor slurry of the lithium element-containing crystal material can effectively reduce the internal resistance of the battery, and can improve the lithium ion content of the battery, thereby improving the conductivity. The functional nano conductor slurry provided by the invention has the characteristics of large specific surface area and high porosity, and is convenient for lithium ion conduction.
In order to better understand the technical solution provided by the present invention, the following description will respectively illustrate the specific processes for preparing functional nano-conductor paste by using several methods provided by the above embodiments of the present invention, and the method and battery characteristics for applying the same to a lithium battery by using a plurality of specific examples.
Example 1
The embodiment provides a preparation method and a performance test result of functional nano conductor slurry.
Adding 2500g of styrene-butadiene rubber and 500g of sodium carboxymethylcellulose into 80L of deionized water, and dispersing at the dispersion speed of 1000rpm for 1 hour; and carrying out ultrasonic treatment on the dispersed slurry for 0.5 hour at the ultrasonic frequency of 5kHz to obtain first slurry.
10000g of functional powder material lithium aluminum titanium phosphate, 500g of polyethylene glycol and 500g of sodium dodecyl benzene sulfonate are added into the first slurry, and are dispersed for 1.5 hours at the dispersion speed of 2000rpm
Adding the dispersed slurry into a centrifuge for centrifugation for 0.5 hour, and adding the slurry into a sand mill for sand milling for 1 hour;
after sand grinding, taking out, adding 1000g of conductive carbon black (SP) and 500g of polyoxyethylene alkylphenol ether, and stirring and dispersing to obtain second slurry; wherein the stirring speed is 50rpm, and the dispersing speed is 1000 rpm;
and carrying out ultrasonic treatment on the second slurry for 0.5 hour at the ultrasonic frequency of 8kHz to obtain the required functional nano conductor slurry.
Fig. 2 shows the results of the first cycle charge and discharge curves of the functional nano-conductor slurry coated on a copper foil and tested using lithium metal as a counter electrode. The discharge specific capacity is 484mAh/g, and the charge specific capacity is 125 mAh/g.
Example 2
The embodiment provides a preparation method and a performance test result of functional nano conductor slurry.
Adding 1kg of functional powder material lithium lanthanum zirconium oxide into 30L of N-methylpyrrolidone solvent, carrying out centrifugal treatment for 30 minutes at the centrifugal speed of 1500rpm, adding the upper layer slurry into a sand mill, carrying out sand grinding for 30 minutes, carrying out ultrasonic treatment for 30 minutes, and carrying out ultrasonic frequency of 3KHz to obtain the functional nano conductor slurry.
The functional nano conductor slurry prepared in the embodiment is used as a coating material of a positive electrode material.
The functional nano conductor slurry prepared above and commercial lithium iron phosphate were mixed, dried and sintered to obtain the coated modified lithium iron phosphate material of the present example 2.
And mixing the coated and modified lithium iron phosphate material serving as the positive electrode material with a binder polyvinylidene fluoride (PVDF) and a conductive additive graphite conductive agent KS-6, and coating the mixture on a copper foil to prepare the pole piece.
In addition, the pole pieces made of the coated and modified lithium iron phosphate material and the commercial lithium iron phosphate material which is not coated and modified by the functional nano conductor slurry according to the present embodiment were assembled into a half cell according to the above method at a test temperature of 45 ℃, 4.2V, and a rate of 1C, and the results are shown in fig. 3. The functional nano conductor slurry coating modified material provided by the invention has more excellent cycle performance. In the fortieth week, the capacity retention rate of the coated and modified lithium iron phosphate material is 92%, and the capacity retention rate of the commercialized lithium iron phosphate material is 64%.
Example 3
The embodiment provides a preparation method of functional nano conductor slurry.
50g of polytetrafluoroethylene binder was added to 10L of Dimethylformamide (DMF) solvent,
dispersing at a dispersion speed of 1000rpm for 1 hour; and carrying out ultrasonic treatment on the slurry for 0.5 hour at an ultrasonic frequency of 5kHz to obtain first slurry.
Slowly adding 30g of polyvinylpyrrolidone and 1kg of functional powder material lithium-aluminum-titanium oxide into the first slurry, carrying out centrifugal treatment for 30 minutes at the centrifugal speed of 1500rpm, then adding the upper layer slurry into a sand mill, carrying out sand grinding for 1 hour, carrying out ultrasonic treatment for 0.5 hour at the ultrasonic frequency of 5000Hz, and obtaining the functional nano conductor slurry.
Example 4
The embodiment provides a preparation method of functional nano conductor slurry.
Adding 1kg of functional powder material lithium zirconium phosphate into 30L of alcohol solvent, and dispersing for 1.5 hours at the dispersion speed of 2000 rpm; and adding a centrifugal machine, carrying out centrifugal treatment for 30 minutes at the centrifugal speed of 1500rpm, adding the upper-layer slurry into a sand mill, sanding for 1 hour, carrying out ultrasonic treatment for 0.5 hour at the ultrasonic frequency of 5000Hz, and obtaining the functional nano conductor slurry.
Example 5
The embodiment provides a preparation method and a performance test result of functional nano conductor slurry.
260g of polyvinylidene fluoride as a binder was added to 5.2kg of N-methylpyrrolidone solvent, and dispersed at a dispersion rate of 5000rpm for 0.5 hour; and carrying out ultrasonic treatment on the dispersed slurry for 0.5 hour at the ultrasonic frequency of 10kHz to obtain first slurry.
Slowly adding 1kg of functional powder material zirconium lithium phosphate into the first slurry, carrying out centrifugal treatment for 30 minutes at the centrifugal speed of 1000rpm, adding the upper layer slurry into a sand mill, carrying out sand grinding for 30 minutes, carrying out ultrasonic treatment for 30 minutes at the ultrasonic frequency of 3000Hz, and obtaining the ionic conductor slurry.
The functional nano conductor slurry is adoptedCoating the solution on the surface of a separator to a thickness of 2 μm, assembling a lithium-copper button cell, and then performing electrochemical plating at a current density of 3mA/cm2The cycle test was conducted under the conditions of (1). Meanwhile, a commercial separator not coated with the functional nano-conductor paste was used as a comparative example, and the test was assembled under the same conditions, and the result was compared as shown in fig. 4. It can be seen that the material of this embodiment has a smaller dc internal resistance. The ac internal resistance of example 5 was 75 ohms and that of the commercial membrane was around 107 ohms.
Example 6
The embodiment provides a preparation method of functional nano conductor slurry.
50g of binder carboxymethyl cellulose was added to 4kg of deionized water, dispersed at a dispersion speed of 2000rmp for 1 hour, and the dispersed slurry was subjected to ultrasonic treatment for 0.5 hour at an ultrasonic frequency of 10kHz to obtain a first slurry.
Slowly adding 1kg of functional powder material zirconium lithium silicate, 25g of dispersing agent sodium dodecyl sulfate and 25g of sodium hexametaphosphate into the first slurry, carrying out centrifugal treatment for 30 minutes under the condition of a centrifugal speed of 1000rpm, adding the centrifuged upper layer slurry into a sand mill, sanding for 1 hour, adding 50g of alkylphenol ethoxylate after completion, placing the slurry into a beater, dispersing and stirring for 1 hour at a stirring speed of 20rpm and a dispersion speed of 3000rpm, adding 100g of styrene butadiene rubber, stirring for 30 minutes at a stirring speed of 20rpm and a dispersion speed of 3000rpm, and obtaining a second slurry. And carrying out ultrasonic treatment on the second slurry for 30 minutes at an ultrasonic frequency of 3000Hz to obtain the functional nano conductor slurry.
Example 7
The embodiment provides a preparation method of functional nano conductor slurry.
260g of a binder polyvinylidene fluoride-hexafluoropropylene copolymer is added into 5.2kg of a dimethylformamide solvent, dispersed for 1 hour at a dispersion speed of 2000rmp, and the dispersed slurry is subjected to ultrasonic treatment for 0.5 hour at an ultrasonic frequency of 10kHz to obtain a first slurry.
Slowly adding 1kg of functional powder material lithium calcium tantalum oxygen into the first slurry, carrying out centrifugal treatment for 30 minutes at a centrifugal speed of 1000rpm, adding the centrifuged upper layer slurry into a sand mill, carrying out sand grinding for 30 minutes, carrying out ultrasonic treatment for 30 minutes at an ultrasonic frequency of 3000Hz, and thus obtaining the functional nano conductor slurry.
Example 8
The embodiment provides a preparation method of functional nano conductor slurry.
260g of adhesive polymethyl methacrylate-butyl acrylate is added into 5.2kg of ethyl acetate solvent, dispersed for 1 hour at the dispersion speed of 1000rmp, and the dispersed slurry is subjected to ultrasonic treatment for 0.5 hour at the ultrasonic frequency of 10kHz to obtain first slurry.
Slowly adding 1kg of functional powder material lithium lanthanum niobium oxygen into the first slurry, carrying out centrifugal treatment for 30 minutes at the centrifugal speed of 1000rpm, adding the centrifuged upper layer slurry into a sand mill, carrying out sand grinding for 30 minutes, carrying out ultrasonic treatment for 30 minutes at the ultrasonic frequency of 3000Hz, and thus obtaining the functional nano conductor slurry.
Example 9
The embodiment provides a preparation method of functional nano conductor slurry.
50g of binder carboxymethyl cellulose was added to 4kg of deionized water, dispersed at a dispersion speed of 2000rmp for 1 hour, and the dispersed slurry was subjected to ultrasonic treatment for 0.5 hour at an ultrasonic frequency of 10kHz to obtain a first slurry.
Slowly adding 1kg of functional powder material lithium zinc phosphate and a dispersing agent, namely 25g of sodium dodecyl sulfate and 25g of sodium hexametaphosphate, into the first slurry, centrifuging for 30 minutes under the condition of a centrifugal speed of 1000rpm, then adding the centrifuged upper layer slurry into a sand mill, sanding for 1 hour, adding 50g of conductive material Carbon Nanotubes (CNTs) after the centrifugation is finished, adding 50g of sodium lauryl sulfate into a beater, stirring and dispersing for 1 hour at a stirring speed of 20rpm and a dispersion speed of 3000rpm, and obtaining a second slurry. And carrying out ultrasonic treatment on the second slurry for 30 minutes at an ultrasonic frequency of 3000Hz to obtain the functional nano conductor slurry.
Example 10
The embodiment provides a preparation method of functional nano conductor slurry.
Adding 50g of styrene butadiene rubber serving as a binder into 5kg of deionized water, stirring at a stirring speed of 30rmp for 1 hour, and carrying out ultrasonic treatment on the dispersed slurry for 0.5 hour at an ultrasonic frequency of 10kHz to obtain first slurry.
Slowly adding 1kg of functional powder material zirconium lithium phosphate and 50g of anti-settling agent polyoxyethylene fatty amine alcohol into the first slurry, carrying out centrifugal treatment for 30 minutes under the condition of a centrifugal speed of 1000rpm, adding the upper layer slurry into a sand mill, sanding for 1 hour, adding 25g of dispersing agent sodium hexametaphosphate after completion, adding conductive material copper powder, putting into a beater, stirring and dispersing for 1 hour at a stirring speed of 20rpm and a dispersing speed of 3000rpm, and obtaining second slurry. And carrying out ultrasonic treatment on the second slurry for 30 minutes at an ultrasonic frequency of 3000Hz to obtain the functional nano conductor slurry.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are merely exemplary embodiments of the present invention, and are not intended to limit the scope of the present invention, and any modifications, equivalent substitutions, improvements and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (10)
1. The functional nano conductor slurry is characterized by comprising the following components in parts by mass: 20 wt% -99.95 wt% of solvent and 0.05 wt% -80 wt% of solute;
wherein the solute comprises 0.05 wt% -79.98 wt% of functional powder material, 0 wt% -79.95 wt% of oxide powder material, 0 wt% -2 wt% of anti-settling agent, 0 wt% -20 wt% of binder, 0 wt% -20 wt% of dispersing agent, 0 wt% -5 wt% of conductive agent and 0 wt% -2 wt% of auxiliary agent;
the functional powder material comprises a lithium-containing crystal material, wherein lithium ions occupy one or more combinations of tetrahedral sites, octahedral sites or hexadecahedral sites of the crystal structure; in the functional powder material, the lithium ion conductivity is more than or equal to 10-6S·cm-1An order of magnitude;
the functional nano conductor slurry is used for any one of a diaphragm coating material, a positive electrode material coating material, a negative electrode material coating material, a positive electrode material additive, a negative electrode material additive or a solid electrolyte additive.
2. The functional nanoconductor paste according to claim 1, wherein the lithium-containing crystal material further contains titanium; wherein in the titanium element, the mass ratio of tetravalent titanium accounts for 3-30%.
3. The functional nanoconductor paste according to claim 1, wherein the lithium-containing crystalline material comprises: one or more of lithium lanthanum zirconium oxide, lithium lanthanum niobium oxide, lithium lanthanum tantalum oxide, lithium titanium silicate, lithium titanium aluminum phosphate, lithium lanthanum titanium oxide, lithium aluminum titanium oxide, zirconium lithium phosphate, lithium zinc phosphate, lithium calcium titanium oxide and zirconium lithium silicate.
4. The functional nanoconductor paste of claim 1,
the oxide powder material comprises: one or more of aluminum oxide, boron oxide, silicon oxide, phosphorus pentoxide, magnesium oxide, zirconium oxide, calcium oxide, sodium oxide and potassium oxide; the particle size of the oxide powder material is between 1nm and 100 um;
the anti-settling agent comprises: one or more of polyamide wax, polyoxyethylene fatty amine alcohol, polyoxyethylene fatty alcohol sulfate, nano-cellulose, polyglycol ether or titanate coupling agent;
the adhesive comprises: one or more of polyvinylidene fluoride, polyvinylidene fluoride-hexafluoropropylene copolymer, carboxymethyl cellulose, sodium carboxymethyl cellulose, polymethyl methacrylate, polyacrylonitrile, styrene butadiene rubber, polyvinyl alcohol, polytetrafluoroethylene, polyolefins, fluorinated rubber, sodium alginate, polyacrylamide, polymethyl methacrylate-butyl acrylate, ethylene-vinyl acetate copolymer, polyvinyl acetate or polyurethane or gelatin;
the dispersant comprises: one or more of sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, sodium dodecyl phosphate, sodium hexametaphosphate, polyacrylic acid, polybutyl acrylate-styrene-acrylic acid, hexadecyl trimethyl ammonium bromide, polyethylene glycol, polyvinylpyrrolidone, polyacrylate, polymethacrylate, maleic anhydride-styrene copolymer, octyl phenol polyoxyethylene ether, monoglyceride, glyceryl tristearate, oleic acid acyl, sodium linoleate, tannic acid, sodium pyrophosphate or succinic acid;
the conductive agent includes: one or more of a graphite conductive agent, conductive carbon black, graphene or metal powder; the graphite conductive agent includes: one or more of KS-6, KS-15, SFG-6 and SFG-15; the conductive carbon black comprises: one or more of acetylene black, Super P, Super S, 350G, carbon fiber VGCF, carbon nanotube CNTs, Ketjen black and activated carbon; the metal powder includes: one or more of zinc powder, copper powder, aluminum powder, silver powder, gold powder, tungsten powder and tin powder;
the auxiliary agent comprises: one or more of polydimethylsiloxane, isophorone, diacetone alcohol, Solvesso150, silicone oil, polyethers, sodium alkyl polyoxyethylene ether carboxylate, polyoxyethylene ether, polyoxyethylene alkylphenol ether, sodium alkyl benzene sulfonate, alkylphenol polyoxyethylene ether, polyoxyethylene alkylamine, sodium lauryl sulfate or polyoxyethylene amide.
5. The functional nanoconductor paste of claim 1, wherein the solvent comprises: one or more of deionized water, alcohol, N-methyl pyrrolidone, tetrahydrofuran, dimethylformamide, isopropanol, ethyl acetate or acetone.
6. A method for preparing the functional nano-conductor paste according to claim 1, wherein the method comprises:
adding 0 wt% -20 wt% of binder, 0 wt% -2 wt% of anti-settling agent and solvent of the functional nano conductor slurry into a pre-stirring tank according to the required proportion by the total mass part of solute in the required functional nano conductor slurry, and dispersing for 0.5-1.5 hours at the dispersion speed of 1000-5000 rpm to obtain uniformly dispersed slurry; wherein the solvent accounts for 20-99.95 wt% of the total mass of the functional nano conductor slurry; the solute accounts for 0.05 to 80 weight percent of the total mass of the functional nano conductor slurry;
carrying out ultrasonic treatment on the slurry for 0.5-1.0 h at an ultrasonic frequency of 1-10 kHz to obtain first slurry;
adding 0.05-79.98 wt% of functional powder material, 0-79.95 wt% of oxide powder material and 0-20 wt% of dispersing agent into the first slurry according to the required proportion, dispersing for 0.5-1.5 hours at the dispersion speed of 1000-5000 rpm, adding a centrifuge for centrifugation for 0.5-1.0 hour, and adding the centrifuged upper slurry into a sand mill for sand milling for 0.5-1.5 hours; the functional powder material comprises a lithium-containing crystal material, wherein lithium ions occupy one or more combinations of tetrahedral sites, octahedral sites or hexadecahedral sites of the crystal structure; in the functional powder material, the lithium ion conductivity is more than or equal to 10-6S·cm-1An order of magnitude;
taking out the materials by sanding, adding 0-5 wt% of conductive agent and 0-2 wt% of auxiliary agent, stirring and dispersing to obtain second slurry; wherein the stirring speed is 10rpm-50rpm, and the dispersing speed is 1000rpm-5000 rpm;
and carrying out ultrasonic treatment on the second slurry for 0.5-1.0 hour at the ultrasonic frequency of 1-10 kHz to obtain the required functional nano conductor slurry.
7. The method according to claim 6, wherein the particle size of the functional powder material and the particle size of the oxide powder material are both 1nm to 100 um.
8. The method according to claim 6, wherein the lithium element-containing crystalline material further contains a tetravalent titanium element; the mass ratio of tetravalent titanium element content in the functional powder material is 3-30%.
9. The method according to claim 6, wherein the lithium-containing crystalline material comprises: one or more of lithium lanthanum zirconium oxide, lithium lanthanum niobium oxide, lithium lanthanum tantalum oxide, lithium titanium silicate, lithium titanium aluminum phosphate, lithium lanthanum titanium oxide, lithium aluminum titanium oxide, zirconium lithium phosphate, lithium zinc phosphate, lithium calcium titanium oxide and zirconium lithium silicate;
the oxide powder material comprises: one or more of aluminum oxide, boron oxide, silicon oxide, phosphorus pentoxide, magnesium oxide, zirconium oxide, calcium oxide, sodium oxide and potassium oxide; the particle size of the oxide powder material is between 1nm and 100 um;
the anti-settling agent comprises: one or more of polyamide wax, polyoxyethylene fatty amine alcohol, polyoxyethylene fatty alcohol sulfate, nano-cellulose, polyglycol ether or titanate coupling agent;
the adhesive comprises: one or more of polyvinylidene fluoride, polyvinylidene fluoride-hexafluoropropylene copolymer, carboxymethyl cellulose, sodium carboxymethyl cellulose, polymethyl methacrylate, polyacrylonitrile, styrene butadiene rubber, polyvinyl alcohol, polytetrafluoroethylene, polyolefins, fluorinated rubber, sodium alginate, polyacrylamide, polymethyl methacrylate-butyl acrylate, ethylene-vinyl acetate copolymer, polyvinyl acetate or polyurethane or gelatin;
the dispersant comprises: one or more of sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, sodium dodecyl phosphate, sodium hexametaphosphate, polyacrylic acid, polybutyl acrylate-styrene-acrylic acid, hexadecyl trimethyl ammonium bromide, polyethylene glycol, polyvinylpyrrolidone, polyacrylate, polymethacrylate, maleic anhydride-styrene copolymer, octyl phenol polyoxyethylene ether, monoglyceride, glyceryl tristearate, oleic acid acyl, sodium linoleate, tannic acid, sodium pyrophosphate or succinic acid;
the conductive agent includes: one or more of a graphite conductive agent, conductive carbon black, graphene or metal powder; the graphite conductive agent includes: one or more of KS-6, KS-15, SFG-6 and SFG-15; the conductive carbon black comprises: one or more of acetylene black, Super P, Super S, 350G, carbon fiber VGCF, carbon nanotube CNTs, Ketjen black and activated carbon; the metal powder includes: one or more of zinc powder, copper powder, aluminum powder, silver powder, gold powder, tungsten powder and tin powder;
the auxiliary agent comprises: one or more of polydimethylsiloxane, isophorone, diacetone alcohol, Solvesso150, silicone oil, polyethers, sodium alkyl polyoxyethylene ether carboxylate, polyoxyethylene ether, polyoxyethylene alkylphenol ether, sodium alkyl benzene sulfonate, alkylphenol polyoxyethylene ether, polyoxyethylene alkylamine, sodium lauryl sulfate or polyoxyethylene amide;
the solvent comprises: one or more of deionized water, alcohol, N-methyl pyrrolidone, tetrahydrofuran, dimethylformamide, isopropanol, ethyl acetate or acetone.
10. A lithium battery comprising the functional nanoconductor paste according to any one of claims 1 to 5.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112876901A (en) * | 2021-02-07 | 2021-06-01 | 中北大学 | Water-dispersible functional ceramic ink and preparation and application thereof |
| CN113451581A (en) * | 2021-07-12 | 2021-09-28 | 珠海冠宇电池股份有限公司 | Negative plate and lithium ion battery comprising same |
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2020
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112876901A (en) * | 2021-02-07 | 2021-06-01 | 中北大学 | Water-dispersible functional ceramic ink and preparation and application thereof |
| CN112876901B (en) * | 2021-02-07 | 2022-11-15 | 中北大学 | Water-dispersible functional ceramic ink and preparation and application thereof |
| CN113451581A (en) * | 2021-07-12 | 2021-09-28 | 珠海冠宇电池股份有限公司 | Negative plate and lithium ion battery comprising same |
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Application publication date: 20200818 |