CN112151745A - Positive electrode material layer for semi-solid battery, preparation method of positive electrode material layer, positive plate and semi-solid battery - Google Patents
Positive electrode material layer for semi-solid battery, preparation method of positive electrode material layer, positive plate and semi-solid battery Download PDFInfo
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- CN112151745A CN112151745A CN202011173590.XA CN202011173590A CN112151745A CN 112151745 A CN112151745 A CN 112151745A CN 202011173590 A CN202011173590 A CN 202011173590A CN 112151745 A CN112151745 A CN 112151745A
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- DEUISMFZZMAAOJ-UHFFFAOYSA-N lithium dihydrogen borate oxalic acid Chemical compound B([O-])(O)O.C(C(=O)O)(=O)O.C(C(=O)O)(=O)O.[Li+] DEUISMFZZMAAOJ-UHFFFAOYSA-N 0.000 claims description 2
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 2
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 2
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/043—Processes of manufacture in general involving compressing or compaction
- H01M4/0435—Rolling or calendering
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
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- H01M2004/021—Physical characteristics, e.g. porosity, surface area
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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- 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
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Abstract
The invention discloses a positive electrode material layer for a semi-solid battery, a preparation method thereof, a positive plate and the semi-solid battery, wherein the method comprises the following steps: 1) mixing the fiberizable polymer powder, the positive active material coated by the polymer electrolyte and the conductive agent, and then drawing the fiberizable polymer powder into fibers under the action of shearing force to obtain a mixture; 2) and carrying out hot-pressing treatment on the mixture on a current collector to a preset thickness to obtain the anode material layer. The method provided by the invention solves the problems of uneven mixing of the positive electrode material and cracking of the pole piece caused by large positive electrode material ratio and high hardness in the dry method preparation of the positive electrode material layer, reduces the requirement on the material of the roll shaft of the roll press in the dry method preparation process of the positive electrode piece, and reduces the equipment cost. The ionic conductivity of the pole piece is increased, the using amount of electrolyte is reduced, and the safety performance of the battery is improved.
Description
Technical Field
The invention relates to the technical field of new energy, and relates to a positive electrode material layer for a semi-solid battery, a preparation method of the positive electrode material layer, a positive plate and a battery.
Background
With the mass popularization of electronic products, lithium batteries are increasingly gaining attention due to their advantages of light weight, small size, high operating voltage, high energy density, large output power, high charging efficiency, no memory effect, and the like. Inevitably, the requirements on the safety and performance of lithium batteries are also higher and higher, and therefore, the improvement of the safety performance of the batteries is also one of the main targets of the future lithium ion battery research. Currently, commercially available lithium ion batteries are liquid electrolyte batteries, and the liquid electrolyte generally consists of lithium salt, an organic solvent and an additive, and is in a liquid state that is easy to flow at room temperature. After the battery is subjected to a strong impact or the inside of the battery swells, the battery package is easily broken and the liquid electrolyte leaks out. Since the liquid electrolyte contains a large amount of flammable and explosive organic solvents, great potential safety hazards are generated.
Although wet coating processes (such as CN1722496A and CN101887970A) adopted in the preparation of the positive electrode in the existing battery are continuously optimized, the processes and equipment have already reached a very mature stage, but it is undeniable that complicated processes such as drying, solvent recovery and reprocessing are required after the wet coating, the costs of manpower and material resources are increased, and the manufacturing cost of the battery is difficult to reduce.
Compared with the traditional wet coating process, many companies and scientific research units focus on a dry electrode preparation technology in a supercapacitor product production process, the preparation of a pole piece can be completed only by mixing an active substance and a binder and then carrying out hot rolling, and an NMP solvent addition and drying recovery process is not needed in the preparation process, so that the preparation process of the pole piece is greatly simplified, the battery manufacturing cost can be greatly reduced, meanwhile, no harmful solvent is used in the whole process, and the problem of environmental pollution caused in the battery manufacturing process is solved.
However, the technology conversion process from the super capacitor to the preparation of the pole piece of the lithium ion battery is still in the initial stage of research and development, and many problems are urgently needed to be solved, for example, in the preparation process of the positive pole piece, because the positive active material has a relatively large specific gravity, the positive material, the conductive agent and the binding agent are difficult to be uniformly mixed in the material mixing process, and the material has relatively large hardness, so that the material is difficult to be pressed into a soft self-supporting film in the pole piece rolling process, cracks are easy to generate, and cannot be compounded with a current collector, and the material with relatively large hardness has too high requirement on the roller shaft material of a roller press, so that the roller shaft is easy to be pressed out of a pit, and the equipment.
Therefore, it is necessary to provide a new method for preparing a pole piece, which reduces the environmental pollution problem caused by battery manufacturing, reduces the cost, and improves the safety performance of the battery.
Disclosure of Invention
In view of the above problems in the prior art, an object of the present invention is to provide a positive electrode material layer, a method of preparing the same, a positive electrode sheet, and a semi-solid battery.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a method for preparing a positive electrode material layer, the method comprising the steps of:
(1) mixing the fiberizable polymer powder, the positive active material coated by the polymer electrolyte and the conductive agent, and then drawing the fiberizable polymer powder into fibers under the action of shearing force to obtain a mixture;
(2) and (2) carrying out hot-pressing treatment on the mixture obtained in the step (1) on a current collector to a preset thickness to obtain the anode material layer, wherein the anode material layer is a self-supporting film and has good flexibility.
In the method, the dry mixing is carried out in the step (1), the fiberizable polymer powder, the polymer electrolyte coated positive active material and the conductive agent are mixed, the fiberizable polymer powder is drawn into fibers under the action of shearing force, the dry powder with certain viscosity is prepared, the drawing degree is not particularly limited, and the mixture is bonded into a mass. Step (2) hot-pressing to prepare a film, namely pressing the powder mixed by the dry method into a positive electrode material layer with a certain thickness in a certain hot-pressing mode; in the hot pressing process, the polymer fibers are mutually overlapped, extruded and moved to form a network structure, and the network structure wraps and bonds other component particles together to form a self-supporting membrane, namely the anode material layer.
In the method, the positive active substance coated by the polymer electrolyte is applied to the preparation of the positive material layer by the dry method, so that on one hand, the polymer electrolyte has good flexibility, and the flexibility of the positive active substance coated by the polymer electrolyte on the polymer electrolyte layer is improved, so that the uniformity of mixed materials can be improved, the hardness of the positive material can be effectively reduced, and the flexibility of the pole piece is improved. The problems of uneven material mixing of the positive electrode material and cracking of the pole piece caused by large positive electrode material ratio and high hardness in the process of preparing the positive electrode material layer by a dry method are solved, the requirement on the material of the roll shaft of the roll press in the preparation process of the positive electrode piece by the dry method can be reduced, and the equipment cost is reduced. On the other hand, the polymer electrolyte has good ion conductivity, the positive active material coated by the polymer electrolyte increases the ionic conductivity of the pole piece, reduces the using amount of electrolyte, and improves the safety performance of the battery.
The diaphragm prepared by the method has good ductility and strong plasticity, can reach higher compaction density through repeated rolling, and can effectively improve the energy density of the battery.
The method is different from the method for preparing the pole piece by a wet method, and the dry method has no addition of an organic solvent, so that the drying process is omitted, the problems of post-treatment, recovery and the like of the organic solvent are avoided, the production cost is effectively saved, and the environmental pollution is avoided. Moreover, because no solvent is added, the solubility between the polymer electrolyte and the solvent does not need to be considered, the optional range of the polymer electrolyte is increased, the further optimization of the battery formula is facilitated, and the battery performance is improved.
The method disclosed by the invention is simple in preparation process and easy to amplify, is a method suitable for industrial application, is beneficial to promoting the development of new energy industry, and has a wide application prospect.
The following is a preferred technical solution of the present invention, but not a limitation to the technical solution provided by the present invention, and the technical objects and advantageous effects of the present invention can be better achieved and achieved by the following preferred technical solution.
Preferably, the fiberizable polymer comprises at least one of Polytetrafluoroethylene (PTFE), Styrene Butadiene Rubber (SBR), Polyimide (PAN), polypropylene (PP), Polyethylene (PE) and Nitrile Butadiene Rubber (NBR), preferably PTFE.
Preferably, the polymer electrolyte-coated positive electrode active material includes a positive electrode active material and a polymer electrolyte layer coated on a surface of the positive electrode active material.
The type of the positive electrode active material is not limited in the invention, and the positive electrode active material commonly used in the field is all applicable to the invention, and can be a doped positive electrode active material or an undoped positive electrode active material, and can typically but not limited by Li1+x1NiyCozMntMsO2-、LiMx2Mn2-x2O4、LiFe1-x3Mx3PO4、Li2Fe1-x4Mx4SiO4And LiFe1- x5Mx5SO4At least one of F, wherein x1 is more than or equal to 0 and less than or equal to 1, Y is more than or equal to 0 and less than or equal to 1, z is more than or equal to 0 and less than or equal to 1, t is more than or equal to 0 and less than or equal to 1, s is more than or equal to 0 and less than or equal to 1, 0 is more than or equal to 0 and less than or equal to 0.2, x2 is more than or equal to 0 and less than or equal to 1, x3 is more than or equal to 0 and less than or equal to 1, and M is selected from Li, Na, K, Mg, Ca, Sr, Ba, Al, Ga, In, Si, Ge, Sn, Pb, Sc, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Ru, Pd, Ag, Cd, La, Ce, Pr, Nd, Sm, Eu, Gd, Er, Tm, Yb, Lu, W.
Preferably, the positive electrode active material is LiCoO2、LiNiO2、LiFePO4、LiNi0.5Mn0.5O2、Li(NiCoMn)1/3O2、Li1.2Ni0.13Mn0.54Co0.13O2And LiMn2O4At least one of;
preferably, the polymer electrolyte layer includes a polymer and an electrolyte salt.
Preferably, in the polymer electrolyte layer, the polymer includes at least one of polymethyl methacrylate (PMMA), Polyacrylonitrile (PAN), polyoxypropylene (PPO), Polyoxyethylene (PEO), polyvinyl chloride (PVC), polyvinylidene fluoride (PVDF), and derivatives thereof. The derivative can be obtained by copolymerizing, crosslinking or blending at least one of the substances and/or monomers.
Preferably, in the polymer electrolyte layer, the electrolyte salt includes at least one of lithium trifluoromethanesulfonate, lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate, lithium dioxalate borate and lithium bis fluorosulfonylimide.
Preferably, the polymer electrolyte layer of the positive electrode active material is contained in an amount of 1% to 30% by mass, for example, 1%, 2%, 2.5%, 3.5%, 4%, 5%, 6.5%, 7%, 8%, 9%, 10%, 13%, 15%, 20%, 23%, 26%, 30% or the like, preferably 3% to 10% by mass.
Preferably, the conductive agent includes at least one of acetylene black, Super-P, carbon nanotube, carbon fiber, ketjen black, graphite, and graphene.
Preferably, the mixture of step (1) has a fiberizable polymer content of 1-30% by weight, for example 1%, 2%, 5%, 7%, 8%, 10%, 12%, 15%, 18%, 20%, 25% or 30%, etc., preferably 3-10%.
Preferably, in the mixture of step (1), the mass ratio of the polymer electrolyte coated positive electrode active material is 25% to 98.5%, for example, 25%, 27%, 30%, 33%, 36%, 40%, 45%, 48%, 50%, 55%, 60%, 63%, 66%, 70%, 75%, 80%, 85%, 90%, 96%, 98%, or the like, preferably 67.5% to 96%.
Preferably, in the mixture of step (1), the conductive agent accounts for 0.5-5% by mass, such as 0.5%, 1%, 1.5%, 2%, 3%, 4%, or 5%, and preferably 1-2.5%.
As a preferred embodiment of the method of the present invention, the mixing speed in step (1) is less than 1000rpm, for example, 100rpm, 150rpm, 200rpm, 300rpm, 350rpm, 450rpm, 500rpm, 600rpm, 700rpm, 800rpm, 900rpm, etc., preferably 100rpm to 800 rpm. The advantage of forming fibres by first mixing the raw materials at a relatively low rotational speed and then drawing the fiberizable polymer powder under the action of shear forces is that: the components are uniformly mixed by low-speed mixing, and then wire drawing is carried out, so that the sufficiency of wire drawing and the uniformity of the components can be ensured.
Preferably, in the mixing process in the step (1), the positive electrode active material coated with the polymer electrolyte and the conductive agent are firstly mixed, and then the polymer powder capable of being fiberized is added for secondary mixing. According to the preferred technical scheme, the raw materials except the fiberizable polymer powder are firstly mixed at one time, and then the fiberizable polymer powder is added for subsequent wire drawing and fiberization, so that the uniformity and the wire drawing sufficiency of all materials can be better ensured.
Preferably, the step (1) of drawing the fiberizable polymer powder under shear force to form fibers comprises: at least one of high-speed stirring, screw extrusion and air flow crushing, and a mashing machine, a high-speed dispersing machine, a twin-screw extruder, an air flow crusher, and the like may be used as the equipment. However, the present invention is not limited to the above-mentioned embodiments, and other embodiments for achieving the object of fiberization are also applicable to the present invention.
Preferably, the manner in which the fiberizable polymer powder is drawn into fibers under the action of the shear force in step (1) is high speed agitation at a speed of > 1000rpm, such as 2000rpm, 3000rpm, 4000rpm, 5000rpm, 6000rpm, 7000rpm, 8000rpm, 9000rpm, 10000rpm, 12000rpm, 12500rpm, 13500rpm, 15000rpm, 16500rpm, 18000rpm, 20000rpm, 21000rpm, 22500rpm, 25000rpm, or the like.
Preferably, the high speed stirring is at a speed of 8000rpm to 25000rpm, such as 8000rpm, 9000rpm, 10000rpm, 11000rpm, 12000rpm, 13000rpm, 15000rpm, 17500rpm, 18500rpm, 20000rpm, 21000rpm, 22500rpm, 23500rpm, 25000rpm, etc., preferably at a speed of 17000rpm to 21000 rpm.
Preferably, the high speed stirring time is 2min to 2h, such as 2min, 5min, 10min, 15min, 17min, 20min, 25min, 28min, 30min, 40min, 50min, 1h, 1.1h, 1.2h, 1.3h, 1.5h, 1.8h or 2h, etc., preferably 10min to 30 min.
In the invention, the purpose of high-speed stirring is to realize uniform mixing of materials on one hand and more importantly to realize fiberization by drawing fiberizable polymers under the action of ultra-strong high-speed dispersion on the other hand. If the speed is too low, the generated shearing force is small, on one hand, the mixing time is too long, the time cost is increased, and on the other hand, the fiberization effect is not ideal; if the speed is too high, the generated shearing force is large, so that the loss of the equipment is large, the service life of the equipment is shortened, and the performance of the temperature-sensitive raw material is possibly deteriorated due to the heat generation problem.
The form of the hot pressing treatment in step (2) is not limited in the present invention, and for example, a roller press may be used to perform hot rolling at a certain temperature.
Preferably, the hot pressing treatment in step (2) is performed at a temperature of 25 ℃ to 300 ℃, for example, 25 ℃, 30 ℃, 35 ℃, 40 ℃, 50 ℃, 65 ℃, 80 ℃, 100 ℃, 115 ℃, 130 ℃, 150 ℃, 180 ℃, 200 ℃, 220 ℃, 230 ℃, 240 ℃ or 250 ℃, etc., preferably at a temperature of 60 ℃ to 250 ℃, and more preferably at a temperature of 140 ℃ to 200 ℃.
Preferably, the predetermined thickness of step (2) is 30um-500um, such as 1um, 3um, 5um, 8um, 12um, 15um, 20um, 25um, 30um, 35um, 40um, 45um, 50um, 55um, 60um, 65um, 70um, 75um, 78um, 82um, 85um, 90um, 100um, 120um, 135um, 150um, 170um, 200um, 225um, 260um, 300um, 350um, 400um, 450um or 500um, etc.
As a further preferred technical solution of the method of the present invention, the method comprises the steps of:
(1) mixing the positive active substance coated by the polymer electrolyte and the conductive agent at a low speed under the condition of 100rpm-800rpm, then adding the fiberizable polymer powder, continuously mixing at the low speed at the original rotating speed, and then stirring at the rotating speed of 8000rpm-25000rpm for 2min-2h to obtain a uniformly mixed mixture;
in the mixture, the mass percentage of the fiberizable polymer powder is 1-30%, the mass percentage of the polymer electrolyte coated positive active substance is 25-98.5%, and the mass percentage of the conductive agent is 0.5-5%;
(2) and (2) carrying out hot-pressing treatment on the mixture obtained in the step (1), wherein the hot-pressing temperature is 60-250 ℃ until the thickness is 30-500 um, and thus obtaining the anode material layer.
In a second aspect, the invention provides a positive electrode material layer, and the positive electrode sheet is prepared by the method in the first aspect.
In a third aspect, the present invention provides a positive electrode sheet comprising the positive electrode material layer according to the second aspect.
Preferably, the positive electrode sheet comprises a current collector and a positive electrode material layer according to claim 8 on the surface of the current collector.
Preferably, the current collector comprises an aluminum foil.
The preparation method of the positive plate is not limited, and the current collector (such as aluminum foil) can be combined with the positive material layer in the hot pressing process, for example, the mixture is paved on the surface of the current collector for hot pressing, so that the positive material layer is formed and the combination of the positive material layer and the positive material layer is realized. The positive electrode material layer may be prepared according to the method of the second aspect, that is, a self-supporting positive electrode material layer is obtained, and then the positive electrode material layer and a current collector (e.g., an aluminum foil) are hot-pressed (e.g., hot-rolled by using a roller press) to achieve the combination of the positive electrode material layer and the current collector. The skilled person can select the material according to the needs, and more preferably, the self-supporting positive electrode material layer is prepared first, and then the two are compounded by hot compaction.
In a fourth aspect, the present invention provides a semi-solid battery comprising the positive electrode tab of the third aspect.
The specific type of the semi-solid battery of the present invention is not limited, and may be any one of a lithium metal battery, a lithium ion battery, a lithium air battery, and a lithium sulfur battery, for example.
Compared with the prior art, the invention has the following beneficial effects:
in the method, the positive active substance coated by the polymer electrolyte is applied to the preparation of the positive material layer by the dry method, so that the polymer electrolyte layer has good flexibility, the uniformity of mixed materials can be improved, the hardness of the positive material can be effectively reduced, and the softness of the pole piece is improved. The problems of uneven material mixing of the positive electrode material and cracking of the pole piece caused by large positive electrode material ratio and high hardness in the process of preparing the positive electrode material layer by a dry method are solved, the requirement on the material of the roll shaft of the roll press in the preparation process of the positive electrode piece by the dry method can be reduced, and the equipment cost is reduced. On the other hand, the polymer electrolyte has good ion conductivity, the positive active material coated by the polymer electrolyte increases the ionic conductivity of the pole piece, reduces the using amount of electrolyte, and improves the safety performance of the battery.
The diaphragm prepared by the method has good ductility and strong plasticity, can reach higher compaction density through repeated rolling, and can effectively improve the energy density of the battery.
The method is different from the method for preparing the pole piece by a wet method, and the dry method has no addition of an organic solvent, so that the drying process is omitted, the problems of post-treatment, recovery and the like of the organic solvent are avoided, the production cost is effectively saved, and the environmental pollution is avoided. Moreover, because no solvent is added, the solubility between the polymer electrolyte and the solvent does not need to be considered, the optional range of the polymer electrolyte is increased, the further optimization of the battery formula is facilitated, and the battery performance is improved.
The method disclosed by the invention is simple in preparation process and easy to amplify, is a method suitable for industrial application, is beneficial to promoting the development of new energy industry, and has a wide application prospect.
Drawings
Fig. 1 is a pictorial representation of a self-supporting positive electrode material layer prepared in example 1.
Fig. 2 is a physical diagram of the positive electrode material layer prepared in comparative example 2.
Detailed Description
The technical scheme of the invention is further explained by the specific implementation mode in combination with the attached drawings.
Example 1
Adding 9g of polymer electrolyte coated nickel cobalt lithium manganate and 0.2g of acetylene black into a stirrer, performing low-speed (100rpm) pulse stirring for 10 minutes, uniformly mixing, then adding 0.8g of polytetrafluoroethylene, performing low-speed (100rpm) pulse stirring for 10 minutes, uniformly mixing, performing high-speed (10000rpm) pulse stirring for 30 minutes, and performing a fiberization process. And (2) putting the mixed powder into a roller press, carrying out hot rolling at 150 ℃ to form a self-supporting film, repeatedly rolling to a certain compaction density to obtain a self-supporting positive electrode material layer (see figure 1), and finally carrying out hot rolling and compounding on the self-supporting positive electrode material layer and a current collector to obtain the positive electrode plate.
Wherein the polymer electrolyte coated lithium nickel cobalt manganese oxide comprises lithium nickel cobalt manganese oxide Li (NiCoMn)1/3O2And coated on the Li (NiCoMn)1/3O2The lithium ion battery comprises a polymer electrolyte layer on the surface, wherein the content of the polymer electrolyte layer in nickel cobalt lithium manganate coated by the polymer electrolyte is 2%, the composition of the polymer electrolyte coating layer is PVC and lithium trifluoromethanesulfonate, and the mass ratio of the PVC to the lithium trifluoromethanesulfonate is 5: 1.
Example 2
Adding 8.5g of polymer electrolyte coated nickel cobalt lithium manganate and 0.5g of conductive agent acetylene black into a stirrer, performing low-speed (300rpm) pulse stirring for 10 minutes, uniformly mixing, then adding 10g of polytetrafluoroethylene, performing low-speed (300rpm) pulse stirring for 10 minutes, uniformly mixing, performing high-speed (16000rpm) pulse stirring for 20 minutes, and performing a fiberization process. And putting the mixed powder into a roller press, performing hot rolling at 150 ℃ to form a self-supporting film, repeatedly rolling to a certain compaction density, and finally performing hot rolling compounding with a current collector to obtain the positive plate.
Wherein the polymer electrolyte coated lithium nickel cobalt manganese oxide comprises lithium nickel cobalt manganese oxide Li (NiCoMn)1/3O2And coated on the Li (NiCoMn)1/3O2The lithium ion battery comprises a polymer electrolyte layer on the surface, wherein the content of the polymer electrolyte layer in nickel cobalt lithium manganate coated by the polymer electrolyte is 3%, the composition of the polymer electrolyte coating layer is polyacrylonitrile and lithium trifluoromethanesulfonate, and the mass ratio of the polyacrylonitrile to the lithium trifluoromethanesulfonate is 6: 1.
Example 3
Adding 8.0g of polymer electrolyte coated nickel cobalt lithium manganate and 0.2g of conductive agent Super-P into a stirrer, performing low-speed (200rpm) pulse stirring for 10 minutes, uniformly mixing, then adding 0.8g of polytetrafluoroethylene, performing low-speed (200rpm) pulse stirring for 10 minutes, uniformly mixing, performing high-speed (17000rpm) pulse stirring for 30 minutes, and performing a fiberization process. And putting the mixed powder into a roller press, performing hot rolling at 130 ℃ to form a self-supporting film, repeatedly rolling to a certain compaction density, and finally performing hot rolling compounding with a current collector to obtain the positive plate.
Wherein the polymer electrolyte coated lithium nickel cobalt manganese oxide comprises lithium nickel cobalt manganese oxide Li (NiCoMn)1/3O2And coated on the Li (NiCoMn)1/3O2The lithium ion battery comprises a polymer electrolyte layer on the surface, wherein the content of the polymer electrolyte layer in nickel cobalt lithium manganate coated by the polymer electrolyte is 3%, the polymer electrolyte layer comprises polymethyl methacrylate, lithium hexafluorophosphate and lithium trifluoromethanesulfonate, and the mass ratio of the polymethyl methacrylate to the lithium hexafluorophosphate to the lithium trifluoromethanesulfonate is 6:0.5: 1.
Example 4
The difference from example 1 is that the content of the polymer electrolyte layer in the polymer electrolyte-coated lithium nickel cobalt manganese oxide was 0.5%.
Example 5
The difference from example 1 is that the content of the polymer electrolyte layer in the polymer electrolyte-coated lithium nickel cobalt manganese oxide was 15%.
Comparative example 1
The types and the contents of the polymer electrolyte coated nickel cobalt lithium manganate and the conductive agent are the same as those in the embodiment 1, polyvinylidene fluoride (PVDF-HSV900) is used as a binder, N-methyl pyrrolidone is used as a solvent, and the processes of homogenizing, wet coating, drying, rolling and the like are carried out to form the positive plate.
Comparative example 2
The difference from example 1 is that the polymer electrolyte-coated lithium nickel cobalt manganese oxide was replaced with lithium nickel cobalt manganese oxide which was not coated with a polymer electrolyte.
And (3) testing:
the positive plates of the above examples and comparative examples were assembled to discharge lithium, the separator was a PE film, and the electrolyte was LiPF6(concentration 1M in electrolyte) is dissolved in a mixed solution of Ethylene Carbonate (EC)/dimethyl carbonate (DEC)/Ethyl Methyl Carbonate (EMC) with a volume ratio of 1:1:1, the addition amount of the electrolyte is half of the volume of the liquid battery (1g/Ah), and charging and discharging are carried out at 0.1C, and the test results are shown in Table 1.
TABLE 1
As can be seen from table 1, the positive electrode material coated with the polymer electrolyte can obtain good dispersibility of the positive electrode material and flexibility of the electrode sheet by using a dry process, and the compacted density of the electrode sheet can be improved compared with a wet coating process, and the corresponding specific discharge capacity and the first effect are both improved;
it can be known from the comparison between example 1 and examples 4 to 5 that the polymer electrolyte coating amount of the polymer electrolyte coated positive active material has an important influence on the product performance, and if the polymer electrolyte coating layer content is too low, the effects of improving the dispersibility of the positive active material and reducing the hardness are limited, the effects of improving the dispersibility of the positive material and reducing the hardness to avoid the electrode sheet cracking in the dry film forming are not good, and the electrochemical performance is reduced. If the content of the polymer electrolyte coating layer is too high, the capacity and the first effect of the positive electrode material are influenced.
As can be seen from the comparison between example 1 and comparative example 1, the method of the present invention and the wet coating process can improve the compacted density of the pole piece, and the corresponding specific discharge capacity and first efficiency are both improved.
As can be seen from the comparison between example 1 and comparative example 2, the uncoated positive electrode material has a large number of cracks on the surface of the electrode sheet prepared by the dry process (see fig. 2), and cannot be used normally.
It can be seen from the comparison between example 1 and comparative examples 1-2 that, in the positive electrode material coated with the polymer electrolyte, no matter the dry-process pole piece preparation process or the wet-process coating process is used, the electrochemical performance is not reduced but improved after the electrolyte content is reduced by half compared with the uncoated positive electrode material.
The applicant states that the present invention is illustrated in detail by the above examples, but the present invention is not limited to the above detailed methods, i.e. it is not meant that the present invention must rely on the above detailed methods for its implementation. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (10)
1. A method for preparing a positive electrode material layer is characterized by comprising the following steps:
(1) mixing the fiberizable polymer powder, the positive active material coated by the polymer electrolyte and the conductive agent, and then drawing the fiberizable polymer powder into fibers under the action of shearing force to obtain a mixture;
(2) and (3) carrying out hot-pressing treatment on the mixture obtained in the step (1) on a current collector to a preset thickness to obtain the anode material layer.
2. The method of claim 1, wherein the fiberizable polymer comprises at least one of Polytetrafluoroethylene (PTFE), Styrene Butadiene Rubber (SBR), Polyimide (PAN), polypropylene (PP), Polyethylene (PE) and Nitrile Butadiene Rubber (NBR), preferably PTFE;
preferably, the positive electrode active material coated with the polymer electrolyte comprises a positive electrode active material and a polymer electrolyte layer coated on the surface of the positive electrode active material;
preferably, the positive electrode active material includes Li1+x1NiyCozMntMsO2-、LiMx2Mn2-x2O4、LiFe1-x3Mx3PO4、Li2Fe1-x4Mx4SiO4And LiFe1-x5Mx5SO4At least one of F, wherein x1 is more than or equal to 0 and less than or equal to 1, Y is more than or equal to 0 and less than or equal to 1, z is more than or equal to 0 and less than or equal to 1, t is more than or equal to 0 and less than or equal to 1, s is more than or equal to 0 and less than or equal to 1, 0 is more than or equal to 0 and less than or equal to 0.2, x2 is more than or equal to 0 and less than or equal to 1, x3 is more than or equal to 0 and less than or equal to 1, and M is selected from Li, Na, K, Mg, Ca, Sr, Ba, Al, Ga, In, Si, Ge, Sn, Pb, Sc, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Ru, Pd, Ag, Cd, La, Ce, Pr, Nd, Sm, Eu, Gd, Er, Tm, Yb, Lu;
preferably, the positive electrode active material is LiCoO2、LiNiO2、LiFePO4、LiNi0.5Mn0.5O2、Li(NiCoMn)1/3O2、Li1.2Ni0.13Mn0.54Co0.13O2And LiMn2O4At least one of;
preferably, the polymer electrolyte layer includes a polymer and an electrolyte salt;
preferably, in the polymer electrolyte layer, the polymer comprises at least one of polymethyl methacrylate (PMMA), Polyacrylonitrile (PAN), polypropylene oxide (PPO), polyethylene oxide (PEO), polyvinyl chloride (PVC), polyvinylidene fluoride (PVDF) and derivatives of the above substances;
preferably, in the polymer electrolyte layer, the electrolyte salt includes at least one of lithium trifluoromethanesulfonate, lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate, lithium dioxalate borate and lithium bis-fluorosulfonylimide;
preferably, in the positive electrode active material coated with the polymer electrolyte, the mass percentage of the polymer electrolyte layer is 1-30%, and preferably 3-10%;
preferably, the conductive agent includes at least one of acetylene black, Super-P, carbon nanotube, carbon fiber, ketjen black, graphite, and graphene.
3. The method according to claim 1 or 2, characterized in that in the mixture of step (1), the mass proportion of the fiberizable polymer is 1-30%, preferably 3-10%;
preferably, in the mixture obtained in the step (1), the mass ratio of the polymer electrolyte coated positive electrode active material is 25% -98.5%, and preferably 67.5% -96%;
preferably, in the mixture in the step (1), the mass ratio of the conductive agent is 0.5-5%, preferably 1-2.5%.
4. The process according to any one of claims 1 to 3, wherein the mixing of step (1) is carried out at a speed of less than 1000rpm, preferably from 100rpm to 800 rpm;
preferably, in the mixing process in the step (1), the positive electrode active material coated with the polymer electrolyte and the conductive agent are firstly mixed, and then the polymer powder capable of being fiberized is added for secondary mixing.
5. The method of any one of claims 1-4, wherein the drawing of the fiberizable polymer powder under shear to form fibers in step (1) comprises: at least one of high-speed stirring, screw extrusion and airflow crushing, preferably high-speed stirring, wherein the high-speed stirring speed is more than or equal to 1000 rpm;
preferably, the high speed stirring speed is 8000rpm-25000rpm, preferably 17000rpm-21000 rpm;
preferably, the time for stirring and mixing at high speed is 2min-2h, preferably 10min-30 min.
6. The method according to any one of claims 1 to 5, wherein the hot pressing treatment of step (2) is hot rolling;
preferably, the temperature of the hot pressing treatment in the step (2) is 25-300 ℃, preferably 60-250 ℃, and further preferably 140-200 ℃;
preferably, the preset thickness of step (2) is 30um-500 um.
7. Method according to any of claims 1-6, characterized in that the method comprises the steps of:
(1) mixing the positive active substance coated by the polymer electrolyte and the conductive agent at a low speed under the condition of 100rpm-800rpm, then adding the fiberizable polymer powder, continuously mixing at the low speed at the original rotating speed, and then stirring at the rotating speed of 8000rpm-25000rpm for 2min-2h to obtain a uniformly mixed mixture;
in the mixture, the mass percentage of the fiberizable polymer powder is 1-30%, the mass percentage of the polymer electrolyte coated positive active substance is 25-98.5%, and the mass percentage of the conductive agent is 0.5-5%;
(2) and (2) carrying out hot-pressing treatment on the mixture obtained in the step (1), wherein the hot-pressing temperature is 60-250 ℃ until the thickness is 30-500 um, and thus obtaining the anode material layer.
8. A positive electrode material layer, characterized in that the positive electrode sheet is produced by the method according to any one of claims 1 to 7.
9. A positive electrode sheet, characterized in that it comprises the positive electrode material layer according to claim 8;
preferably, the positive electrode sheet comprises a current collector and a positive electrode material layer according to claim 8 on the surface of the current collector;
preferably, the current collector comprises an aluminum foil.
10. A semi-solid battery, characterized in that it comprises the positive electrode sheet of claim 9;
preferably, the semi-solid state battery includes any one of a lithium metal battery, a lithium ion battery, a lithium air battery, and a lithium sulfur battery.
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| CN113921767A (en) * | 2021-09-29 | 2022-01-11 | 蜂巢能源科技有限公司 | Positive pole piece for solid-state battery and preparation method and application thereof |
| CN113921749A (en) * | 2021-10-13 | 2022-01-11 | 深圳市今朝时代股份有限公司 | Method for preparing electrode slice by directly pressing film |
| CN114188515A (en) * | 2021-11-23 | 2022-03-15 | 厦门大学 | Polymer-coated high-nickel ternary cathode material and preparation method and application thereof |
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