Method of preparing electrode assemblies
Provided herein a method of preparing electrode assemblies for lithium-ion batteries. The method disclosed herein comprises a step of pre-drying separator in the battery manufacturing process before the stacking step, thereby significantly lowering the water content of the separator. Therefore, separators can be used to prepare electrode assemblies regardless of conditions under which they are stored or transported. In addition, the peeling strength between the porous base material and protective porous layer is largely unaffected by the drying process disclosed herein.
1. A method of preparing an electrode assembly, comprising the steps of:
1) preparing a slurry comprising a conductive agent, an active battery electrode material and a binder material;
2) applying the slurry on a current collector to form a coated film on the current collector;
3) drying the coated film on the current collector;
4) pre-drying a coated separator comprising a porous base material and a protective porous layer coated on one or both surfaces of the porous base material under vacuum at a temperature from about 80° C. to about 150° C. wherein the separator has a melting point of 160° C. or higher, and wherein the water content of the separator before pre-drying is above 500 ppm by weight, based on the total weight of the separator before pre-drying;
5) stacking at least one anode, at least one cathode, and at least one pre-dried separator interposed between the at least one anode and at least one cathode, wherein the water content of the pre-dried separator is less than 60 ppm by weight, based on the total weight of the pre-dried separator; and
6) drying the electrode assembly;
wherein the porous base material comprises polymeric fibers selected from the group consisting of polyacetal, polyamide, polycarbonate, polyamide, polyetherether ketone, polysulfones, polyphenylene oxide, polyphenylene sulfide, polyacrylonitrile, polyvinylidene fluoride, polyvinyl pyrrolidone, polyester, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalene, polybutvlene naphthalate, and combinations thereof;
wherein the protective porous layer comprises an inorganic filler selected from the group consisting of Al 2 O 3 , SiO 2 , TiO 2 , ZrO 2 , BaO x , ZnO, CaCO 3 , TiN, AlN, MTiO 3 , K 2 O.nTiO 2 , Na 2 O.mTiO 2 , and combinations thereof, wherein x is 1 or 2; M is Ba, Sr or Ca; n is 1, 2, 4, 6 or 8; and m is 3 or 6; and
wherein the peeling strengths of the separator before pre-drying and the pre-dried separator are independently between 0.05 N/cm and 0.25 N/cm.
2. The method of claim 1 , wherein the porous base material of the separator has a melting point of 200° C. or higher.
3. The method of claim 1 , wherein the separator is pre-dried for a time period from about 2 hours to about 12 hours, or from about 2 hours to about 8 hours.
4. The method of claim 1 , wherein the separator is pre-dried under a pressure of less than 25 kPa, less than 15 kPa, less than 10 kPa, or less than 5 kPa.
5. The method of claim 1 , wherein the protective porous layer further comprises a binder material selected from the group consisting of styrene-butadiene rubber, acrylated styrene-butadiene rubber, acrylonitrile copolymer, acrylonitrile-butadiene rubber, nitrile butadiene rubber, acrylonitrile-styrene-butadiene copolymer, acryl rubber, butyl rubber, fluorine rubber, polytetrafluoroethylene, polyethylene, polypropylene, ethylene/propylene copolymers, polybutadiene, polyethylene oxide, chlorosulfonated polyethylene, polyvinylpyrrolidone, polyvinylpyridine, polyvinyl alcohol, polyvinyl acetate, polyepichlorohydrin, polyphosphazene, polyacrylonitrile, polystyrene, latex, acrylic resins, phenolic resins, epoxy resins, carboxymethyl cellulose, hydroxypropyl cellulose, cellulose acetate, cellulose acetate butyrate, cellulose acetate propionate, cyanoethylcellulose, cyanoethylsucrose, polyester, polyamide, polyether, polyimide, polycarboxylate, polycarboxylic acid, polyacrylic acid, polyacrylate, polymethacrylic acid, polymethacrylate, polyacrylamide, polyurethane, fluorinated polymer, chlorinated polymer, a salt of alginic acid, polyvinylidene fluoride, poly(vinylidene fluoride)-hexafluoropropene, and combinations thereof.
6. The method of claim 5 , wherein the weight ratio of the inorganic filler to the binder material is from about 99:1 to about 1:1.
7. The method of claim 1 , wherein the separator has a thickness from about 1 μm to about 80 μm.
8. The method of claim 1 , wherein the separator has a porosity from about 40% to about 97%.
9. The method of claim 1 , wherein the active battery electrode material is a cathode material selected from group consisting of LiCoO 2 , LiNiO 2 , LiNi x Mn y O 2 , Li 1+z Ni x Mn y Co 1-x-y O 2 , LiNi x Co y Al z O 2 , LiV 2 O 5 , LiTiS 2 , LiMoS 2 , LiMnO 2 , LiCrO 2 , LiMn 2 O 4 , LiFeO 2 , LiFePO 4 , and combinations thereof, wherein each x is independently from 0.3 to 0.8; each y is independently from 0.1 to 0.45; and each z is independently from 0 to 0.2.
10. The method of claim 1 , wherein the conductive agent is selected from the group consisting of carbon, carbon black, graphite, expanded graphite, graphene, graphene nanoplatelets, carbon fibres, carbon nano-fibers, graphitized carbon flake, carbon tubes, carbon nanotubes, activated carbon, mesoporous carbon, and combinations thereof.
11. The method of claim 1 , wherein the electrode assembly is dried under a pressure of less than 25 kPa, less than 15 kPa, less than 10 kPa, or less than 5 kPa.
12. The method of claim 1 , wherein the electrode assembly is dried for a time period from about 2 hours to about 24 hours, or from about 4 hours to about 12 hours.
13. The method of claim 1 , wherein the electrode assembly is dried at a temperature from about 70° C. to about 150° C.
14. The method of claim 1 , wherein the water content of the pre-dried separator is less than 50 ppm by weight, based on the total weight of the pre-dried separator.
15. The method of claim 1 , wherein the water content of the dried electrode assembly is less than 20 ppm by weight, based on the total weight of the dried electrode assembly.
16. A lithium battery comprising the electrode assembly prepared by the method of claim 1 .