CN115692703B - Battery binder, battery cathode, battery and preparation method of battery binder - Google Patents
Battery binder, battery cathode, battery and preparation method of battery binder Download PDFInfo
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- CN115692703B CN115692703B CN202211406846.6A CN202211406846A CN115692703B CN 115692703 B CN115692703 B CN 115692703B CN 202211406846 A CN202211406846 A CN 202211406846A CN 115692703 B CN115692703 B CN 115692703B
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- battery
- acid
- binder
- battery binder
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- 239000011230 binding agent Substances 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- DCEMCPAKSGRHCN-UHFFFAOYSA-N oxirane-2,3-dicarboxylic acid Chemical compound OC(=O)C1OC1C(O)=O DCEMCPAKSGRHCN-UHFFFAOYSA-N 0.000 claims abstract description 32
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 22
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 22
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 15
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- 239000002904 solvent Substances 0.000 claims abstract description 11
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- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 4
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- CYUUZGXOQDCCGH-UHFFFAOYSA-N dodecyl dodecanoate Chemical compound CCCCCCCCCCCCOC(=O)CCCCCCCCCCC CYUUZGXOQDCCGH-UHFFFAOYSA-N 0.000 claims description 9
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- 239000003049 inorganic solvent Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- GNVXPFBEZCSHQZ-UHFFFAOYSA-N iron(2+);sulfide Chemical compound [S-2].[Fe+2] GNVXPFBEZCSHQZ-UHFFFAOYSA-N 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 239000001989 lithium alloy Substances 0.000 description 1
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910001537 lithium tetrachloroaluminate Inorganic materials 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- 229910000614 lithium tin phosphorous sulfides (LSPS) Inorganic materials 0.000 description 1
- ZJZXSOKJEJFHCP-UHFFFAOYSA-M lithium;thiocyanate Chemical compound [Li+].[S-]C#N ZJZXSOKJEJFHCP-UHFFFAOYSA-M 0.000 description 1
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 229940017219 methyl propionate Drugs 0.000 description 1
- MPDOUGUGIVBSGZ-UHFFFAOYSA-N n-(cyclobutylmethyl)-3-(trifluoromethyl)aniline Chemical compound FC(F)(F)C1=CC=CC(NCC2CCC2)=C1 MPDOUGUGIVBSGZ-UHFFFAOYSA-N 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 239000010450 olivine Substances 0.000 description 1
- 229910052609 olivine Inorganic materials 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229920005569 poly(vinylidene fluoride-co-hexafluoropropylene) Polymers 0.000 description 1
- 229920000447 polyanionic polymer Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000011866 silicon-based anode active material Substances 0.000 description 1
- 235000002639 sodium chloride Nutrition 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 229910009160 xLi2S Inorganic materials 0.000 description 1
Classifications
-
- 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
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a battery binder, a battery cathode, a battery and a preparation method of the battery binder, and belongs to the technical field of batteries. The preparation method comprises the following steps: adding epoxy succinic acid and a solvent into a container, and mixing to obtain a first solution; adjusting the pH of the first solution to be alkaline to obtain a second solution; adding potassium persulfate into the second solution to obtain a third solution; adding acrylic acid and/or methacrylic acid into the third solution and simultaneously adjusting the pH value of the solution to keep the solution alkaline to obtain a fourth solution; and heating, cooling, diluting, regulating pH and drying the fourth solution to obtain the battery binder. The battery binder provided by the invention can optimize the peeling strength, the first charge and discharge efficiency, the discharge performance and the cycle capacity retention rate of the battery.
Description
Technical Field
The invention relates to the technical field of batteries, in particular to a battery binder, a battery negative electrode, a battery and a preparation method of the battery binder.
Background
The pole piece of the lithium battery comprises a current collector and active substances, wherein the active substances are required to be adhered to the current collector through adhesive, the existing adhesive comprises CMC, PVDF and sodium alginate, and long-term practice shows that the adhesive has poor performances in the aspects of peel strength, expansion, specific capacity and the like of the pole piece. In this regard, there is a method in the prior art that polyacrylic acid (PAA) is used as a binder, and the PAA has a large number of carboxyl groups in the molecular chain, so that a strong hydrogen bond can be formed with the silicon surface, which has been proved to be an ideal binder suitable for high-capacity silicon-based negative electrode materials, and compared with CMC, PVDF and sodium alginate, the PAA has a higher carboxyl group density, and the molecular chain of PAA is easier to implement various modifications. However, it has been found through testing and long-term practice that PAA still has deficiencies in peel strength and cycle capacity retention of the negative electrode.
Therefore, how to provide a new battery binder is a technical problem to be solved by those skilled in the art.
Disclosure of Invention
The invention provides a battery binder, a battery cathode, a battery and a preparation method of the battery binder, which can optimize the peeling strength, the first charge and discharge efficiency, the discharge performance and the cycle capacity retention rate of the battery.
In order to solve one or more of the technical problems, the application adopts the following technical scheme:
In a first aspect, a method for preparing a battery binder is provided, comprising:
adding epoxy succinic acid and a solvent into a container, and mixing to obtain a first solution;
adjusting the pH of the first solution to be alkaline to obtain a second solution;
adding potassium persulfate into the second solution to obtain a third solution;
Adding acrylic acid and/or methacrylic acid into the third solution and simultaneously adjusting the pH value of the solution to keep the solution alkaline to obtain a fourth solution;
And heating, cooling, diluting, regulating pH and drying the fourth solution to obtain the battery binder.
Further, the stoichiometric ratio of the cis-epoxysuccinic acid to the acrylic acid is 0.9 to 1.1.
Further, the epoxysuccinic acid includes cis-epoxysuccinic acid and trans-epoxysuccinic acid.
Further, the battery binder includes a copolymer of polyacrylic acid and succinic acid having the chemical formula:
wherein n is any one of 8 to 10.
Further, the concentration of the first solution is 5-10 mol/L.
Further, the heating, cooling, diluting, adjusting pH, and drying the fourth solution to obtain the battery binder includes:
Heating the fourth solution in a water bath to a preset temperature and then performing constant-temperature reaction until the color of the fourth solution is changed from colorless to yellow;
and cooling and diluting, adjusting the pH value of the fourth solution to be acidic, and then drying to obtain the battery binder.
Further, the adding of acrylic acid and/or methacrylic acid to the third solution comprises:
The acrylic acid and/or methacrylic acid was added dropwise to the third solution using a constant pressure dropping funnel.
In a second aspect, a battery binder is also provided, and the battery binder is prepared by the preparation method.
In a third aspect, there is also provided a battery anode comprising: a current collector, a negative electrode active material, and the battery binder.
In a fourth aspect, there is also provided a battery comprising the battery anode.
The technical scheme provided by the embodiment of the invention has the beneficial effects that:
according to the embodiment of the invention, the copolymer of polyacrylic acid and succinic acid is synthesized by copolymerizing epoxy succinic acid and acrylic acid, so that the carboxyl density of polypropylene is further improved, the peel strength of the pole piece can be improved when the copolymer is used as a binder to be applied to a battery pole piece, the expansion of a silicon-oxygen negative electrode in the circulation process is inhibited, and the specific capacity stability of the electrode in the whole circulation process is obviously improved.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings required for the description of the embodiments will be briefly described below, and it is apparent that the drawings in the following description are only some embodiments of the present application, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
Fig. 1 is a flow chart of a method for preparing a battery binder according to an embodiment of the present invention.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the present invention more apparent, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments of the present invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
As described in the background art, the adhesive for the battery pole piece in the prior art has the defects of being unfavorable for the performance of the pole piece in terms of peeling strength, expansion, specific capacity and the like. In this regard, the preparation method of the battery binder provided by the application utilizes the characteristic that polyacrylic acid contains a large amount of carboxyl groups and can form very strong hydrogen bond action with the silicon surface, and adopts the copolymerization of epoxy succinic acid and acrylic acid to synthesize the copolymer of polyacrylic acid and succinic acid, so that the carboxyl density of polyacrylic acid is further improved, the peel strength of a pole piece is further improved, the expansion of a silicon-oxygen negative electrode in the circulation process is inhibited, and the specific capacity stability of the electrode in the whole circulation process is obviously improved.
Specifically, as an example of the present application, as shown in fig. 1, the preparation method generally includes the steps of:
s10: adding epoxy succinic acid and a solvent into a container, and mixing to obtain a first solution;
Wherein, the epoxy succinic acid can be cis-epoxy succinic acid, trans-epoxy succinic acid, a mixture of the cis-epoxy succinic acid and the trans-epoxy succinic acid, deionized water as a solvent, and other organic or inorganic solvents. In the present application, the concentration of the first solution is 5 to 10mol/L, preferably 6.67mol/L, for example, 0.2mol of epoxysuccinic acid is mixed with 30ml of deionized water, taking the solvent as deionized water.
S20: adjusting the pH of the first solution to be alkaline to obtain a second solution;
Wherein the adjustment of the pH can be accomplished by dropwise addition of NaOH to the solution, in one example, a 40% NaOH aqueous solution is selected to adjust the pH, preferably to about 10 in step S20.
S30: adding potassium persulfate into the second solution to obtain a third solution;
Wherein the potassium persulfate may be a potassium persulfate solution having a concentration of about 2%.
S40: adding acrylic acid and/or methacrylic acid into the third solution and simultaneously adjusting the pH value of the solution to keep the solution alkaline to obtain a fourth solution;
Wherein in one example of the present application, the stoichiometric ratio of the epoxysuccinic acid to the acrylic acid and/or methacrylic acid is 0.9 to 1.1. Preferably, the pH in step S40 is kept weakly alkaline, and the pH is preferably 7 to 8.
S50: and heating, cooling, diluting, regulating pH and drying the fourth solution to obtain the battery binder.
The fourth solution is heated to promote the reaction, and the fourth solution is cooled, diluted, pH-adjusted and dried after the reaction is completed, wherein the dilution may be performed by using a solvent such as ethanol to reduce the viscosity of the reaction system, and the fourth solution may be subjected to still standing precipitation after dilution and before drying, and the precipitate may be dried to obtain a battery binder, and the drying may be performed in a vacuum environment.
Preferably, in one example of the present application, the epoxy succinic acid and acrylic acid (and/or methacrylic acid) react as follows:
wherein n is any one of 8 to 10, and the product can be expressed as Polymer D.
Optionally, in one example of the present application, the step S50 includes:
Heating the fourth solution in a water bath to a preset temperature and then performing constant-temperature reaction until the color of the fourth solution is changed from colorless to yellow;
and cooling and diluting, adjusting the pH value of the fourth solution to be acidic, and then drying to obtain the battery binder.
Wherein the adjustment of the pH can be achieved using aqueous HCl, preferably 1mol/L aqueous HCl, in one example, to a pH of 3.
Preferably, in one example of the present application, the adding acrylic acid and/or methacrylic acid to the third solution includes:
The acrylic acid and/or methacrylic acid was added dropwise to the third solution using a constant pressure dropping funnel.
According to the preparation method, the epoxy succinic acid and the acrylic acid are copolymerized to synthesize the copolymer of the polyacrylic acid and the succinic acid, so that the carboxyl density of the polypropylene is further improved, the peel strength of the pole piece can be improved when the copolymer is used as a binder to be used in a battery pole piece, the expansion of a silicon-oxygen negative electrode in the circulation process is inhibited, and the specific capacity stability of the electrode in the whole circulation process is obviously improved.
The application also provides a battery binder corresponding to the preparation method, which is prepared by adopting the preparation method provided by any one of the examples. The battery binder can be applied to the battery cathode to inhibit the expansion of the silicon-oxygen cathode in the circulation process so as to obviously improve the specific capacity stability of the electrode in the whole circulation process.
The present application also provides a battery anode, which generally includes a current collector, an anode active material, and the battery binder, wherein the battery binder may be applied between the current collector and the anode active material, or may be applied on the current collector together with the anode active material after being mixed.
The negative electrode is formed of a lithium host material that can be used as a negative electrode of a lithium ion battery. For example, the anode may contain an anode active material capable of functioning as an anode electrode of a battery. The anode active material layer may be composed of various anode active materials. In certain embodiments, the negative electrode may further include an electrolyte, such as the oxide, sulfide, halide electrolyte particles noted previously.
The present application is not particularly limited to the anode current collector, and any known anode active material can be used in the present application without departing from the concept of the present application; in one embodiment, the negative electrode current collector includes any one of aluminum, copper, nickel, or zinc alloy.
The kind of the anode active material is not particularly limited in the present application, and any known anode active material can be used in the present application without departing from the concept of the present application; in one embodiment, the negative electrode active material comprises lithium metal and/or a lithium alloy. In other embodiments, the anode is a silicon-based anode active material that includes silicon, such as a silicon alloy, silicon oxide, or a combination thereof, which may also be mixed with graphite in some cases. In other embodiments, the anode may include a carbonaceous-based anode active material comprising one or more of graphite, graphene, carbon Nanotubes (CNTs), and combinations thereof. In yet other embodiments, the negative electrode includes one or more negative electrode active materials that accept lithium, such as lithium titanium oxide (Li 4Ti5O12), one or more transition metals (e.g., tin (Sn)), one or more metal oxides (e.g., vanadium oxide (V 2O5), tin oxide (SnO), titanium dioxide (TiO 2)), titanium niobium oxide (Ti xNbyOz, where 0.ltoreq.x.ltoreq.2, 0.ltoreq.y.ltoreq.24, and 0.ltoreq.z.ltoreq.64), metal alloys (such as copper-tin alloy (Cu 6Sn5)), and one or more metal sulfides (such as iron sulfide (FeS)).
Alternatively, the anode active material in the anode may be doped with one or more conductive agents that provide an electron conduction path. The conductive agent may include carbon-based materials, powdered nickel or other metal particles, or conductive polymers. The carbon-based material may include, for example, particles of carbon black, graphite, superP, acetylene black (such as KETCHENTM black or DENKATM black), carbon fibers and nanotubes, graphene, and the like. Examples of the conductive polymer include polyaniline, polythiophene, polyacetylene, polypyrrole, poly (3, 4-ethylenedioxythiophene) polysulfstyrene, and the like.
In addition to the binders defined in this embodiment, the anode active material in the anode may be mixed with other known polymeric binder materials capable of improving the structural integrity of the anode, for example, alternatively, the binder may be: poly (tetrafluoroethylene) (PTFE), sodium carboxymethyl cellulose (CMC), styrene Butadiene Rubber (SBR), polyvinylidene fluoride (PVDF), nitrile Butadiene Rubber (NBR), styrene butylene styrene copolymer (SEBS), styrene butadiene styrene copolymer (SBS), lithium polyacrylate (LiPAA), sodium polyacrylate (NaPAA), sodium alginate, lithium alginate, and combinations thereof.
The anode may include greater than or equal to about 50wt% to less than or equal to about 97wt% of an anode active material, alternatively greater than or equal to about 0wt% to less than or equal to about 60wt% of a solid state electrolyte, alternatively greater than or equal to about 0wt% to less than or equal to about 15 wt% of a conductive material, and alternatively greater than or equal to about 0wt% to less than or equal to about 10wt% of a binder.
The present application also provides a battery, which generally includes the above battery anode, and inevitably includes other structures or components such as a positive electrode, a separator, and an electrolyte, corresponding to the above battery anode.
Wherein the positive electrode is formed from a plurality of positive electrode active particles comprising one or more transition metal cations, such as manganese (Mn), nickel (Ni), cobalt (Co), chromium (Cr), iron (Fe), vanadium (V), and combinations thereof. In some embodiments, the positive electrode electroactive material layer further comprises an electrolyte, such as a plurality of electrolyte particles. The positive electrode active material layer has a thickness of greater than or equal to about 1 μm to less than or equal to about 1,000 μm.
The positive electroactive material layer is one of a layered oxide cathode, a spinel cathode, and a polyanion cathode. For example, a layered oxide cathode (e.g., a rock salt layered oxide) comprises one or more lithium-based positive electrode active materials selected from the group consisting of: liCoO 2(LCO),LiNixMnyCo1-x-yO2 (wherein 0.ltoreq.x.ltoreq.1 and 0.ltoreq.y.ltoreq.1), liNi 1-x-yCoxAlyO2 (wherein 0.ltoreq.x.ltoreq.1 and 0.ltoreq.y.ltoreq.1), liNi xMn1-xO2 (wherein 0.ltoreq.x.ltoreq.1), and Li 1+xMO2 (wherein M is one of Mn, ni, co and Al and 0.ltoreq.x.ltoreq.1). The spinel cathode comprises one or more lithium-based positive electrode active materials selected from the group consisting of: liMn 2O4 (LMO) and LiNi xMn1.5O4. The olivine cathode comprises one or more lithium-based positive electroactive species LiMPO 4 (where M is at least one of Fe, ni, co, and Mn). The polyanionic cation comprises, for example, phosphates such as LiV 2(PO4)3 and/or silicates such as LiFeSiO 4.
In one embodiment, one or more lithium-based positive electrode electroactive species may optionally be coated (e.g., by LiNbO 3 and/or Al 2O3) and/or may be doped (e.g., by magnesium (Mg)). Further, in certain embodiments, one or more lithium-based positive electrode active materials may optionally be mixed with one or more conductive materials that provide an electron conduction path and/or at least one polymeric binder material that improves the structural integrity of the positive electrode. For example, the positive electrode active material layer may include greater than or equal to about 30wt% to less than or equal to about 98 wt% of one or more lithium-based positive electrode active materials; greater than or equal to about 0wt% to less than or equal to about 30wt% of a conductive agent; and greater than or equal to about 0wt% to less than or equal to about 20wt% of a binder, and in certain aspects, optionally greater than or equal to about 1wt% to less than or equal to about 20wt% of a binder.
The positive electrode active material layer may be optionally mixed with a binder as follows: such as Polytetrafluoroethylene (PTFE), sodium carboxymethylcellulose (CMC), styrene-butadiene rubber (SBR), polyvinylidene fluoride (PVDF), nitrile rubber (NBR), styrene-ethylene-butylene-styrene copolymer (SEBS), styrene-butadiene-styrene copolymer (SBS), lithium polyacrylate (LiPAA), sodium polyacrylate (NaPAA), sodium alginate, lithium alginate, and combinations thereof. The conductive agent may include a carbon-based material, powdered nickel or other metal particles, or a conductive polymer. Carbon-based materials may include, for example, carbon black, graphite, acetylene black (e.g., KETCHENTM black or DENKATM black), carbon fibers and particles of nanotubes, graphene, and the like. Examples of the conductive polymer include polyaniline, polythiophene, polyacetylene, polypyrrole, and the like.
The positive electrode current collector may facilitate the flow of electrons between the positive electrode and an external circuit. The positive current collector may comprise a metal, such as a metal foil, a metal grid or mesh, or a metal mesh. For example, the positive electrode current collector may be formed of aluminum, stainless steel, and/or nickel or any other suitable conductive agent known to those skilled in the art.
The present application is not particularly limited to the barrier film, and any known type of barrier film can be used in the present application, such as a separator suitable for a liquid battery and a solid electrolyte film in a solid battery, without departing from the concept of the present application.
When a liquid battery system is used, the barrier film may be one or more of a polyolefin microporous film, polypropylene, polyethylene felt, glass fiber felt, or ultra fine glass fiber paper.
When the battery is a liquid battery, the electrolyte includes at least a nonaqueous liquid electrolyte solution, and as one embodiment, the electrolyte is composed of only a nonaqueous electrolyte solution including an organic solvent and a lithium salt dissolved in the organic solvent; the present application is not particularly limited in the kind of lithium salt and solvent in which the lithium salt is dissolved, and any known lithium salt and solvent can be used in the present application without departing from the concept of the present application, and as an illustrative example, lithium salts that can be used include: lithium hexafluorophosphate (LiPF 6); lithium perchlorate (LiClO 4), lithium tetrachloroaluminate (LiAlCl 4), lithium iodide (LiI), lithium bromide (LiBr), lithium thiocyanate (LiSCN), lithium tetrafluoroborate (LiBF 4), lithium difluorooxalato borate (LiBF 2(C2O4)) (liodbb), lithium tetraphenylborate (LiB (C 6H5)4), lithium bis (oxalato) borate (LiB (C2O 4)2) (LiBOB), lithium tetrafluorooxalato phosphate (LiPF 4(C2O4)) (LiFOP), lithium nitrate (LiNO 3), lithium hexafluoroarsonate (LiAsF 6), lithium triflate (LiCF 3SO3), lithium bis (trifluoromethanesulfonyl) sulfonate (litfssi) (LiN (CF 3SO2)2), lithium difluorosulfimide (FSO 2)2) (LIFSI), and combinations thereof in certain variations, the lithium salt is selected from the group consisting of lithium hexafluorophosphate (LiPF 6), lithium bis (trifluoromethanesulfonyl) sulfonate (LITFSI) (LiN) (libbc) (3), lithium bis (LiPF 4(C2O4) (lif), lithium carbonate (lif 35 SO), lithium (co-2), lithium (co-carbonate (co) such as lithium carbonate (co-2), lithium carbonate (co-carbonate (co) and (co-2), lithium (co-polymer (co) carbonate) such as, lithium carbonate (co) and the like, lithium carbonate (co-2), and combinations thereof, dimethyl carbonate (DMC), diethyl carbonate (DEC), methyl ethyl carbonate (EMC)), aliphatic carboxylic acid esters (e.g., methyl formate, methyl acetate, methyl propionate), gamma-lactones (e.g., gamma-butyrolactone, gamma-valerolactone), chain structural ethers (e.g., 1, 2-Dimethoxyethane (DME), 1-2-diethoxyethane, ethoxymethoxyethane), cyclic ethers (e.g., tetrahydrofuran, 2-methyltetrahydrofuran), 1, 3-Dioxolane (DOL), sulfur compounds (e.g., sulfolane), and combinations thereof. In a fully nonaqueous electrolyte system, the electrolyte can include the one or more lithium salts at a concentration of greater than or equal to 1M to less than or equal to about 2M. In certain embodiments, for example when the electrolyte has a lithium concentration of greater than about 2M or has an ionic liquid, the electrolyte may include one or more diluents, such as fluorovinyl carbonate (FEC) and/or Hydrofluoroether (HFE).
Particularly preferably, the electrolyte is a solid electrolyte or a combination of both a nonaqueous liquid electrolyte solution and a solid electrolyte.
When the battery is a solid battery or a solid-liquid hybrid battery, the solid electrolyte membrane is required to be used, and can be one or a combination of a plurality of oxide solid electrolyte membrane, sulfide solid electrolyte membrane, halide solid electrolyte membrane and polymer solid electrolyte membrane;
As an embodiment, the polymer solid electrolyte membrane-based component may comprise one or more polymer materials selected from the group consisting of: polyethylene glycol, polyethylene oxide (PEO), poly (p-phenylene oxide) (PPO), poly (methyl methacrylate) (PMMA), polyacrylonitrile (PAN), polyvinylidene fluoride (PVDF), polyvinylidene fluoride co-hexafluoropropylene (PVDF-HFP), polyvinyl chloride (PVC), and combinations thereof. In one variation, the one or more polymeric materials may have an ionic conductivity equal to about 10-4S/cm.
As an embodiment, the oxide solid electrolyte membrane is composed of oxide solid electrolyte particles, and may include one or more of garnet ceramics, LISICON-type oxides, NASICON-type oxides, and perovskite-type ceramics. For example, the one or more garnet ceramics may be selected from the group ：Li6.5La3Zr1.75Te0.25O12、Li7La3Zr2O12、Li6.2Ga0.3La2.95Rb0.05Zr2O12、Li6.85La2.9Ca0.1Zr1.75Nb0.25O12、Li6.25Al0.25La3Zr2O12、Li6.75La3Zr1.75Nb0.25O12、Li6.75La3Zr1.75Nb0.25O12 comprising the following and combinations thereof. The one or more LISICON-type oxides may be selected from the group comprising: li 14Zn(GeO4)4、Li3+x(P1-xSix)O4 (where 0< x < 1), li 3+xGexV1-xO4 (where 0< x < 1), and combinations thereof. One or more NASICON-type oxides may be defined by LiMM '(PO 4)3), where M and M' are independently selected from Al, ge, ti, sn, hf, zr and La., for example, in certain variations, one or more NASICON-type oxides may be selected from the group consisting of Li 1+xAlxGe2-x(PO4)3 (LAGP) (where 0+.ltoreq.x.ltoreq.2), li 1+xAlxTi2-x(PO4)3 (LATP) (where 0+.ltoreq.x.ltoreq.2), li 1+xYxZr2-x(PO4)3 (LYZP) (where 0≤x≤2)、Li1.3Al0.3Ti1.7(PO4)3、LiTi2(PO4)3、LiGeTi(PO4)3、LiGe2(PO4)3、LiHf2(PO4)3 and combinations thereof. One or more perovskite-type ceramics may be selected from the group ：Li3.3La0.53TiO3、LiSr1.65Zr1.3Ta1.7O9、Li2x-ySr1-xTayZr1-yO3( including where x=0.75 y and 0.60<y<0.75)、Li3/8Sr7/16Nb3/4Zr1/4O3、Li3xLa(2/3-x)TiO3( where 0< x < 0.25) and combinations thereof. In one variation, one or more oxide-based materials may have an ionic conductivity of greater than or equal to about 10 "5S/cm to less than or equal to about 10" 1S/cm.
As an embodiment, the sulfide solid electrolyte membrane is composed of sulfide solid electrolyte particles, and may include one or more sulfide-based materials selected from the group consisting of: li 2S-P2S5、Li2S-P2S5-MSx (where M is Si, ge, and Sn and 0≤x≤2)、Li3.4Si0.4P0.6S4、Li10GeP2S11.7O0.3、Li9.6P3S12、Li7P3S11、Li9P3S9O3、Li10.35Si1.35P1.65S12、Li9.81Sn0.81P2.19S12、Li10(Si0.5Ge0.5)P2S12、Li(Ge0.5Sn0.5)P2S12、Li(Si0.5Sn0.5)PsS12、Li10GeP2S12(LGPS)、Li6PS5X( where X is Cl, br, or I)、Li7P2S8I、Li10.35Ge1.35P1.65S12、Li3.25Ge0.25P0.75S4、Li10SnP2S12、Li10SiP2S12、Li9.54Si1.74P1.44S11.7Cl0.3、(1-x)P2S5-xLi2S( where 0.5.ltoreq.x.ltoreq.0.7), and combinations thereof. In one variation, the one or more sulfide-based materials can have an ionic conductivity of greater than or equal to about 10-7S/cm to less than or equal to about 1S/cm.
As an embodiment, the halide solid electrolyte membrane may be composed of halide solid electrolyte particles, including Li2CdCl4、Li2MgCl4、Li2CdI4、Li2ZnI4、Li3OCl、LiI、Li5ZnI4、Li3OCl1-xBrx( where 0< x < 1) and combinations thereof. In one variation, the one or more halide-based materials can have an ionic conductivity of greater than or equal to about 10-8S/cm to less than or equal to about 10-1S/cm.
As one embodiment, the borate solid electrolyte membrane is composed of borate solid electrolyte particles, comprising one or more borate-based materials of the group of: li 2B4O7、Li2O-(B2O3)-(P2O5) and combinations thereof. In one variation, the one or more borate-based materials may have an ionic conductivity of greater than or equal to about 10-7S/cm to less than or equal to about 10-2S/cm.
As one embodiment, the nitride solid electrolyte membrane is composed of nitride solid electrolyte particles, including Li 3N、Li7PN4、LiSi2N3, liPON, and combinations thereof. In one variation, the one or more nitride-based materials may have an ionic conductivity of greater than or equal to about 10-9S/cm to less than or equal to about 1S/cm.
As an embodiment, the hydride solid electrolyte membrane is comprised of hydride solid electrolyte particles, which may comprise one or more hydride-based materials selected from the group consisting of: li 3AlH6、LiBH4、LiBH4-LiX (where X is one of Cl, br, and I), liNH 2、Li2NH、LiBH4-LiNH2, and combinations thereof. In one variation, the one or more hydride-based materials can have an ionic conductivity of greater than or equal to about 10-7S/cm to less than or equal to about 10-2S/cm.
In further variations, the solid electrolyte particles may be a quasi-solid electrolyte comprising a mixture of the nonaqueous liquid electrolyte solution detailed above and the solid electrolyte system, e.g., comprising one or more ionic liquids and one or more metal oxide particles such as alumina (Al 2O3) and/or silica (SiO 2).
Any combination of the above optional solutions may be adopted to form an optional embodiment of the present invention, which is not described herein.
The advantageous effects of the present application will be further described below with reference to examples and comparative examples.
Example 1
1. Polymer D was prepared: adding 0.2mol of cis-epoxysuccinic acid into a three-neck flask, then adding 30ml of deionized water to completely dissolve the cis-epoxysuccinic acid, slowly adding 40% NaOH aqueous solution to adjust the pH value in the flask to about 10 under the condition of maintaining mechanical stirring at 30rpm/min, then adding 2% potassium persulfate, then dropwise adding acrylic acid by using a constant-pressure dropping funnel, and simultaneously dropwise adding 40% NaOH aqueous solution to control the pH value of the solution; after the acrylic acid is added dropwise, the temperature is raised to 90 ℃ by using a water bath, and the reaction is carried out at constant temperature; the viscosity of the reaction system gradually increases along with the progress of the reaction, and the color gradually changes from colorless to yellow; after the reaction is finished, cooling to room temperature by using a water bath, adding a small amount of ethanol for dilution, reducing the viscosity of a reaction system, standing for precipitation, finally adding 1mol/L HCl aqueous solution to adjust the pH value of the whole system to 3, and carrying out vacuum drying to obtain a product Polymer D;
2. preparing a battery:
Dissolving an anode active material, a conductive agent and a binder in a solvent NMP, uniformly stirring, coating on an aluminum foil, and drying to obtain an anode sheet;
and dissolving SiO/C, a conductive agent and Polymer D in a solvent, uniformly stirring to obtain negative electrode slurry, coating the negative electrode slurry on a copper foil, and drying to obtain the negative electrode plate to be supplemented with lithium.
And (3) laminating the positive pole piece, the negative pole piece and the diaphragm, putting the laminated positive pole piece, the laminated negative pole piece and the diaphragm into an aluminum plastic film, and injecting liquid into the aluminum plastic film to obtain the lithium ion battery.
Example 2
The difference from example 1 is that: trans-epoxysuccinic acid was used instead of cis-epoxysuccinic acid.
Example 3
The difference from example 1 is that: methacrylic acid was used instead of acrylic acid.
Comparative example 1
The difference from example 1 is that: polyacrylic acid was used instead of cis-epoxysuccinic acid.
The batteries produced in examples 1 to 3 and comparative example 1 were respectively tested for peel strength, initial charge and discharge efficiency, room temperature 3C rate discharge performance, and room temperature cycle 500-week capacity retention rate.
Test mode of peel strength:
① Cutting the graphite negative electrode plate into long strips with the length of 170mm and the width of 20mm respectively by using a flat paper cutter, and wiping the scale-free steel plate ruler clean by using dust-free paper without leaving dirt and dust;
② Pasting double-sided adhesive tape with the width of 25mm on a non-scale steel plate ruler, wherein the length is 70mm, and the position is centered;
③ Sticking a test sample on a double-sided adhesive tape, enabling end faces to be flush, and rolling the test sample back and forth on the surface of a pole piece for 3 times by using a pressing wheel (2 kg) with the diameter of 84mm and the height of 45 mm;
④ And after the free end of the negative electrode plate in the experimental sample is turned over by 180 degrees, the negative electrode plate is clamped on an upper clamp of a tensile tester, a non-scale steel plate ruler is clamped on a lower clamp, a plurality of negative electrode plates with the width of 20mm are prepared under the conditions that the temperature is 22-28 ℃ and the humidity is less than 25%, the stretching speed of the electrode plates is 200mm/min, the average value of stretching 25-80 mm (the total stretching distance is 100 mm) is tested, the negative electrode plates are peeled, and the test result of the peeling strength of the electrode plate coating is read when the current collector and the coating of the electrode plates are completely separated.
The first charge and discharge efficiency test mode is as follows:
① Charging at 1/3C under room temperature to obtain a final voltage, cutting off the current by 0.05C, recording the charging capacity, and standing for 30min;
② The discharge was performed at 1/3C to a final voltage, and the discharge capacity was recorded, and the first charge-discharge efficiency was obtained by using the discharge capacity to the charge capacity.
Test mode of room temperature 3C rate discharge performance:
charging at 1C under room temperature to a final voltage, stopping current at 0.05C, standing for 30min, discharging at 1C and 3C respectively to a final voltage, recording discharge capacity, and obtaining room temperature 3C rate discharge performance by using 3C discharge capacity to 1C discharge capacity.
Test mode of capacity retention rate of 500 weeks of normal temperature cycle:
① Charging at normal temperature with 1C or prescribed current to a final voltage, cutting off the current by 0.05C, and standing for 30min;
② Discharging at 1C to discharge final pressure, recording discharge capacity, and standing for 30min;
③ And (3) circulating ①～②.
Characterization of the Polymer IR(KBr)υ：3416cm-1(-OH),2940,、2860cm-1(-CH2-),1597cm-1(-C＝O)(-),1113cm-1(-C-O-C-);
1HNMR (400 MHz, D 2 O, ppm) δ:1.19 to 1.23 (carboxyl beta-CH 2), 3.648, 3.650 to 3.71 (carboxyl alpha-CH), 4.56 (carboxyl and carbon oxygen bond together alpha-CH).
The test results are shown in table 1 below.
TABLE 1
From the test results of table 1, it can be seen that:
After the Polymer D obtained by copolymerization of the epoxy succinic acid and the acrylic acid (or methacrylic acid) is used as a battery binder, the peeling strength, the first charge and discharge efficiency, the room-temperature 3C rate discharge performance and the room-temperature cycle 500-week capacity retention rate of the battery can be further optimized on the basis of taking the polyacrylic acid as the binder.
The foregoing description of the preferred embodiments of the invention is not intended to limit the invention to the precise form disclosed, and any such modifications, equivalents, and alternatives falling within the spirit and scope of the invention are intended to be included within the scope of the invention.
Claims (9)
1. A method for preparing a battery binder, comprising:
adding epoxy succinic acid and a solvent into a container, and mixing to obtain a first solution;
adjusting the pH of the first solution to be alkaline to obtain a second solution;
adding potassium persulfate into the second solution to obtain a third solution;
Adding acrylic acid and/or methacrylic acid into the third solution and simultaneously adjusting the pH value of the solution to keep the solution alkaline to obtain a fourth solution;
heating, cooling, diluting, regulating pH and drying the fourth solution to obtain the battery binder;
the heating, cooling, diluting, adjusting the pH and drying the fourth solution to obtain the battery binder comprises the following steps:
Heating the fourth solution in a water bath to a preset temperature, and then performing a constant-temperature reaction, wherein the color of the fourth solution is changed from colorless to yellow along with the gradual increase of the viscosity of a reaction system when the reaction is performed;
and cooling and diluting, adjusting the pH value of the fourth solution to be acidic, and then drying to obtain the battery binder.
2. The process according to claim 1, wherein the stoichiometric ratio of the epoxysuccinic acid to the acrylic acid and/or methacrylic acid is 0.9 to 1.1.
3. The method of claim 1, wherein the epoxysuccinic acid comprises cis-epoxysuccinic acid and trans-epoxysuccinic acid.
4. The method of claim 1, wherein the battery binder comprises a copolymer of acrylic acid and epoxysuccinic acid having the formula:
wherein n is any one of 8 to 10.
5. The method according to claim 1, wherein the concentration of the first solution is 5 to 10mol/L.
6. The method of claim 1, wherein adding acrylic acid and/or methacrylic acid to the third solution comprises:
The acrylic acid and/or methacrylic acid was added dropwise to the third solution using a constant pressure dropping funnel.
7. A battery binder, wherein the battery binder is prepared by the preparation method of any one of claims 1 to 6.
8. A battery anode comprising a current collector, an anode active material, and the battery binder of claim 7.
9. A battery comprising the battery anode of claim 8.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102766232A (en) * | 2012-07-25 | 2012-11-07 | 河北科技大学 | Preparation method of epoxysuccinate /acrylic acid/2-acrylamido-2-methyl propane sulfonic acid copolymer |
| US9109084B1 (en) * | 2014-09-18 | 2015-08-18 | Jacam Chemical Company 2013, Llc | Synthesis of polyepoxy succinic acid compounds using free radical initiators |
| CN109021851A (en) * | 2018-07-04 | 2018-12-18 | 东莞市古川胶带有限公司 | A kind of acrylic protective film and preparation method thereof |
| CN109148886A (en) * | 2018-08-28 | 2019-01-04 | 合肥国轩高科动力能源有限公司 | Binder and preparation method thereof, anode plate for lithium ionic cell |
| CN113773435A (en) * | 2020-06-10 | 2021-12-10 | 恒大新能源技术(深圳)有限公司 | Mussel bionic polymer, silicon-carbon negative electrode binder, silicon-carbon negative electrode material and application |
| CN114350294A (en) * | 2021-04-09 | 2022-04-15 | 杭州安誉科技有限公司 | Preparation method of conductive adhesive film for circuit board |
-
2022
- 2022-11-10 CN CN202211406846.6A patent/CN115692703B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102766232A (en) * | 2012-07-25 | 2012-11-07 | 河北科技大学 | Preparation method of epoxysuccinate /acrylic acid/2-acrylamido-2-methyl propane sulfonic acid copolymer |
| US9109084B1 (en) * | 2014-09-18 | 2015-08-18 | Jacam Chemical Company 2013, Llc | Synthesis of polyepoxy succinic acid compounds using free radical initiators |
| CN109021851A (en) * | 2018-07-04 | 2018-12-18 | 东莞市古川胶带有限公司 | A kind of acrylic protective film and preparation method thereof |
| CN109148886A (en) * | 2018-08-28 | 2019-01-04 | 合肥国轩高科动力能源有限公司 | Binder and preparation method thereof, anode plate for lithium ionic cell |
| CN113773435A (en) * | 2020-06-10 | 2021-12-10 | 恒大新能源技术(深圳)有限公司 | Mussel bionic polymer, silicon-carbon negative electrode binder, silicon-carbon negative electrode material and application |
| CN114350294A (en) * | 2021-04-09 | 2022-04-15 | 杭州安誉科技有限公司 | Preparation method of conductive adhesive film for circuit board |
Non-Patent Citations (2)
| Title |
|---|
| 《环氧琥珀酸与丙烯酸共聚物的合成及性能研究》;王春荣;《中国优秀硕士学位论文全文数据库 工程科技I辑》(第第11期期);第22-27页 * |
| 无影胶在3C行业中的应用及发展;蔡泉;罗顺;李建波;任杰;;中国胶粘剂;第26卷(第03期);第56-59页 * |
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