Ionic conductor slurry, preparation method therefor and application thereof
View Patent ↗An ionic conductor slurry comprised parts by mass: 0.05 wt %-99.98 wt % of an ionic conductor powder material, 0 wt %-2 wt % of an anti-settling agent, 0 wt %-10 wt % of a binder, 0 wt %-2 wt % of dispersant, 0 wt %-2 wt % of an auxiliary agent, and 20 wt %-99.95 wt % of a solvent, wherein the ionic conductor powder material comprises one among the following: a garnet-type solid electrolyte material, a NASICON-type solid electrolyte material, a LISICON-type solid electrolyte material, a perovskite-type solid electrolyte material, and derivatives thereof; The particle size of the ionic conductor powder is between 1 nm to 100 μm; and the ionic conductor slurry is used for separator coating material, positive electrode material coating materials, negative electrode material cladding materials, positive electrode material additive, a negative electrode material additive, polymer solid electrolyte additives, or solid-liquid mixed solid electrolyte.
1. An ionic conductor slurry, comprising, in parts by mass: 0.05 wt %-99.98 wt % of a material of ionic conductor powder, 0.05 wt %-2 wt % of an anti-settling agent, 0 wt %-10 wt % of a binder, 0 wt %-2 wt % of a dispersant, 0 wt %-2 wt % of an auxiliary, and 20 wt %-99.95 wt % of a solvent, wherein the material of ionic conductor powder comprises one of a material of garnet-type solid electrolyte, a material of NASICON-type solid electrolyte, a material of LISICON-type solid electrolyte, a material of perovskite-type solid electrolyte, and a derivative material thereof; a particle size of the ionic conductor powder ranges from 1 nm to 100 μm; wherein the anti-settling agent is polyamide wax, polyoxyethylene fatty alcohol amide, or polyoxyethylene fatty alcohol sulphate; and the ionic conductor slurry is applicable to an anode-material cladding material, a cathode-material cladding material, an anode-material additive, a cathode-material additive, an additive to polymer solid electrolyte, or a solid-liquid hybrid solid electrolyte.
2. The ionic conductor slurry according to claim 1 , wherein:
the garnet-type solid electrolyte is Li 7+m−n−3z A1 z La 3−m A4 m Zr 2−n B4 n O 12 , wherein m, n and z are all in a range of [0-1], A4 is one or more of La, Ca, Sr, Ba, or K, and B4 is one or more of Ta, Nb, W, or a hafnium element Hf;
the LISICON-type solid electrolyte is Li 14 A1(B1O 4 ) 4 , wherein A1 is one or more of Zn, Zr, Cr, or Sn, and B1 is one or more of Ge, Si, S, or P;
the NASICON-type solid electrolyte is Li 1+x A2 x B2 2−x (PO 4 ) 3 , wherein 0.01≤x≤0.5, A2 is one or more of A1, Y, Ga, Cr, In, Fe, Se, or La, and B2 is one or more of Ti, Ge, Ta, Zr, Sn, Fe, V, or the hafnium element Hf; and
the perovskite-type solid electrolyte is Li 3y A3 2/3−y B3O 3 , wherein 0.01≤y≤⅔, A3 is one or more of La, A1, Mg, Fe, or Ta, and B3 is one or more of Ti, Nb, Sr or Pr.
3. The ionic conductor slurry according to claim 1 , wherein the binder comprises one or more of polyvinylidene fluoride, carboxymethylcellulose, sodium carboxymethylcellulose, polymethyl methacrylate, polyacrylonitrile, butadiene styrene rubber, polyvinyl alcohol, polytetrafluoroethylene, polyolefins, fluorinated rubber, sodium alginate, polyacrylamide, polymethylmethacrylate-butyl acrylate, ethylene-vinyl copolymer, polyvinyl acetate, polyurethane, or gelatin.
4. The ionic conductor slurry according to claim 1 , wherein the dispersant comprises one or more of sodium dodecyl benzene sulfonate, lauryl sodium sulfate, sodium hexametaphosphate, polyacrylic acid, cetyl trimethyl ammonium bromide, polyethylene glycol, polyvinylpyrrolidone, potassium polyacrylate, octylphenol polyoxyethylene ether, monoglyceride, glycerol tristearate, acyl oleate, or succinic acid.
5. The ionic conductor slurry according to claim 1 , wherein the auxiliary comprises one or more of polydimethylsiloxane, polyethers, sodium alkyl polyoxyethylene ether carboxylate, polyoxyethylated alkylphenol ether, sodium alkyl benzene sulfonate, alkylphenol polyoxyethylene ether, polyoxyethylene alkyl amine, or polyoxyethylene amide.
6. The ionic conductor slurry according to claim 1 , wherein the solvent comprises one or a mixture of more than one of deionized water, alcohol, N-methylpyrrolidone NMP, tetrahydrofuran, dimethylformamide DMF, or acetone.
7. A preparation method for the ionic conductor slurry according to claim 1 , comprising:
adding 0 wt %-10 wt % of the binder and 20 wt %-99.95 wt % of the solvent to a pre-stirring tank in desired proportions based on total mass parts of the desired ionic conductor slurry, and after the binder is completely dissolved, obtaining a uniform first slurry;
adding 0.05 wt %-99.98 wt % of the material of ionic conductor powder to the first slurry in a desired proportion, adding not more than 2 wt % of the anti-settling agent, and centrifuging at a centrifugal speed of 500 rpm-5000 rpm for 30 min to 1 h, wherein the material of ionic conductor powder comprises one of the material of garnet-type solid electrolyte, the material of NASICON-type solid electrolyte, the material of LISICON-type solid electrolyte, the material of perovskite-type solid electrolyte, and the derivative material thereof, and the particle size of the ionic conductor powder ranges from 1 nm to 100 μm; wherein the anti-settling agent is polyamide wax, polyoxyethylene fatty alcohol amide, or polyoxyethylene fatty alcohol sulphate;
after centrifuging, adding a resultant to a sand mill to be sand milled for 30 min to 1 h;
after sand milling, taking out a resultant, into which 0 wt %-2 wt % of the dispersant and 0 wt %-2 wt % of the auxiliary are added, and stirring and dispersing to obtain a second slurry, wherein a stirring speed is 10 rpm-50 rpm, and a dispersing speed is 1000 rpm-5000 rpm; and
ultrasonically processing the second slurry at an ultrasonic frequency of 1 kHz-10 kHz for 30 min to 1 h to obtain the desired ionic conductor slurry;
wherein the ionic conductor slurry is applicable to an anode-material cladding material, a cathode-material cladding material, an anode-material additive, a cathode-material additive, an additive to polymer solid electrolyte, or a solid-liquid hybrid solid electrolyte.
8. The preparation method for the ionic conductor slurry according to claim 7 , wherein the garnet-type solid electrolyte is Li 7+m−n−3z A1 z La 3−m A4 m Zr 2−n B4 n O 12 , wherein m, n and z are all in a range of [0-1], A4 is one or more of La, Ca, Sr, Ba, or K, and B4 is one or more of Ta, Nb, W, or a hafnium element Hf;
the LISICON-type solid electrolyte is Li 14 A1(B1O 4 ) 4 , wherein A1 is one or more of Zn, Zr, Cr, or Sn, and B1 is one or more of Ge, Si, S, or P;
the NASICON-type solid electrolyte is Li 1+x A2 x B2 2−x (PO 4 ) 3 , wherein 0.01≤x≤0.5, A2 is one or more of A1, Y, Ga, Cr, In, Fe, Se, or La, and B2 is one or more of Ti, Ge, Ta, Zr, Sn, Fe, V, or the hafnium element Hf;
the perovskite-type solid electrolyte is Li 3y A3 2/3−y B3O 3 , wherein 0.01≤y≤⅔, A3 is one or more of La, A1, Mg, Fe, or Ta, and B3 is one or more of Ti, Nb, Sr or Pr;
the binder comprises one or more of polyvinylidene fluoride, carboxymethylcellulose, sodium carboxymethylcellulose, polymethyl methacrylate, polyacrylonitrile, butadiene styrene rubber, polyvinyl alcohol, polytetrafluoroethylene, polyolefins, fluorinated rubber, sodium alginate, polyacrylamide, polymethylmethacrylate-butyl acrylate, ethylene-vinyl copolymer, polyvinyl acetate, polyurethane, or gelatin;
the dispersant comprises one or more of sodium dodecyl benzene sulfonate, lauryl sodium sulfate, sodium hexametaphosphate, polyacrylic acid, cetyl trimethyl ammonium bromide, polyethylene glycol, polyvinylpyrrolidone, potassium polyacrylate, octylphenol polyoxyethylene ether, monoglyceride, glycerol tristearate, acyl oleate, or succinic acid;
the auxiliary comprises one or more of polydimethylsiloxane, polyethers, sodium alkyl polyoxyethylene ether carboxylate, polyoxyethylated alkylphenol ether, sodium alkyl benzene sulfonate, alkylphenol polyoxyethylene ether, polyoxyethylene alkyl amine, or polyoxyethylene amide; and
the solvent comprises one or a mixture of more than one of deionized water, alcohol, N-methylpyrrolidone NMP, tetrahydrofuran, dimethylformamide DMF, or acetone.
9. An application of the ionic conductor slurry according to claim 1 , wherein the ionic conductor slurry is applicable to an energy-storage device and a product containing the energy-storage device; and the energy-storage device comprises one or more of a liquid lithium-ion battery, a metal lithium battery, a solid-liquid hybrid battery, a semisolid battery, or an all-solid-state battery.