CN111384346A - Diaphragm and manufacturing method thereof, battery core and battery - Google Patents

Diaphragm and manufacturing method thereof, battery core and battery Download PDF

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Publication number
CN111384346A
CN111384346A CN202010465971.9A CN202010465971A CN111384346A CN 111384346 A CN111384346 A CN 111384346A CN 202010465971 A CN202010465971 A CN 202010465971A CN 111384346 A CN111384346 A CN 111384346A
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China
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conductor layer
ion conductor
fast ion
inorganic
organic
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Chinese (zh)
Inventor
袁相霏
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Beijing Xiaomi Mobile Software Co Ltd
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Beijing Xiaomi Mobile Software Co Ltd
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Priority to CN202010465971.9A priority Critical patent/CN111384346A/en
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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
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/431—Inorganic material
    • 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
    • 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
    • H01M10/058—Construction or manufacture
    • 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
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/403—Manufacturing processes of separators, membranes or diaphragms
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Cell Separators (AREA)

Abstract

The disclosure provides a diaphragm, a manufacturing method of the diaphragm, a battery core and a battery. The separator is used for a lithium ion battery, and the separator includes: the porous base layer, the first organic fast ion conductor layer, the first inorganic fast ion conductor layer and the second organic fast ion conductor layer. Wherein the porous base layer includes a first side and a second side opposite the first side. The first organic fast ion conductor layer is arranged on the first surface. The first inorganic fast ion conductor layer is arranged on the second surface. The second organic fast ion conductor layer is arranged on one surface of the first inorganic fast ion conductor layer, which faces away from the porous base layer. The diaphragm has good mechanical strength, interface impedance between the diaphragm and the positive pole piece and between the diaphragm and the negative pole piece is small, and the charging speed of the battery core comprising the diaphragm and the lithium ion battery is high, so that the diaphragm is favorable for being applied to quick charging.

Description

Diaphragm and manufacturing method thereof, battery core and battery
Technical Field
The disclosure relates to the technical field of batteries, and in particular relates to a diaphragm, a manufacturing method of the diaphragm, a battery core and a battery.
Background
With the development of the fast charging technology of electronic devices, batteries with a faster charging speed are favored by people. The battery comprises a battery cell, wherein the battery cell comprises a positive pole piece, a negative pole piece and a diaphragm arranged between the positive pole piece and the negative pole piece. However, the compatibility between the diaphragm and the positive electrode plate and between the diaphragm and the negative electrode plate is poor, so that the interface impedance between the diaphragm and the positive electrode plate and between the diaphragm and the negative electrode plate is high, and the diaphragm is not beneficial to the rapid conduction of ions, so that the rapid charging of a battery cell or a battery is not facilitated. Based on this, it is important to provide a separator that facilitates rapid charging of the cell or battery.
Disclosure of Invention
The present disclosure provides an improved separator, a method of manufacturing the same, a cell, and a battery.
One aspect of the present disclosure provides a separator for a battery cell, the separator comprising:
a porous substrate comprising a first side and a second side opposite the first side;
the first organic fast ion conductor layer is arranged on the first surface;
the first inorganic fast ion conductor layer is arranged on the second surface; and
and the second organic fast ion conductor layer is arranged on one surface of the first inorganic fast ion conductor layer, which faces back to the porous base layer.
Optionally, the material of the first organic fast ion conductor layer and the material of the second organic fast ion conductor layer each include at least one of polyethylene oxide and its derivatives, polysiloxane and its derivatives, polymethyl methacrylate and its derivatives, polyacrylate and its derivatives, polyvinyl alcohol and its derivatives, polyvinylidene fluoride and its derivatives, polyhexafluoropropylene and its derivatives, polyvinylidene fluoride-hexafluoropropylene and its derivatives, polyethylene glycol and its derivatives, polytetrafluoroethylene and its derivatives, polyacrylonitrile and its derivatives.
Optionally, the material of the first inorganic fast ion conductor layer includes: at least one of a layered lithium-based electrolyte, an oxide electrolyte, and a sulfide electrolyte.
Optionally, the material of the first inorganic fast ion conductor layer comprises the layered lithium-based electrolyte, which comprises lithium nitride; and/or
The material of the first inorganic fast ion conductor layer comprises the oxide electrolyte, and the oxide electrolyte comprises: at least one of NASICON type, LISICON type, garnet type, LiPON type, perovskite type, and anti-perovskite type; and/or
The material of the first inorganic fast ion conductor layer comprises the sulfide electrolyte, which comprises: li10GeP2S12、Li10GeP2S12Derivative of (5), Li9.54Si1.74P1.44S11.7Cl0.3、Li9.54Si1.74P1.44S11.7Cl0.3Derivative of (5), Li7La3Zr2O12And Li7La3Zr2O12At least one of the derivatives of (1).
Optionally, the thickness of the first organic fast ion conductor layer ranges from 0.5 μm to 10 μm, the thickness of the second organic fast ion conductor layer ranges from 0.5 μm to 10 μm, and the thickness of the first inorganic fast ion conductor layer ranges from 0.5 μm to 10 μm.
Another aspect of the present disclosure provides a manufacturing method of a separator, which is applied to any one of the separators mentioned above, the manufacturing method including:
forming a first organic fast ion conductor layer on the first surface of the porous base layer;
forming a first inorganic fast ion conductor layer on the second surface of the porous base layer;
and forming a second organic fast ion conductor layer on one surface of the first inorganic fast ion conductor layer, which faces away from the porous base layer.
Optionally, the forming a first organic fast ion conductor layer on the first side of the porous base layer includes:
configuring a first mixed slurry comprising a first organic polymer electrolyte, a first additive, and a first solvent, the first additive comprising: at least one of a first binder, a first inorganic filler, and a first plasticizer;
and coating the first mixed slurry on the first surface, and performing first drying treatment to enable the first mixed slurry to form the first organic fast ion conductor layer.
Optionally, the forming a first inorganic fast ion conductor layer on the second surface of the porous base layer includes:
configuring a second mixed slurry comprising an inorganic solid state electrolyte, a second additive, and a second solvent, the second additive comprising: at least one of a second binder, a second inorganic filler, and a second plasticizer;
and coating the second mixed slurry on the second surface, and performing second drying treatment to enable the second mixed slurry to form the first inorganic fast ion conductor layer.
Optionally, the forming a second organic fast ion conductor layer on a side of the first inorganic fast ion conductor layer opposite to the porous base layer includes:
configuring a third mixed slurry comprising a second organic polymer electrolyte, a third additive, and a third solvent, the third additive comprising: at least one of a third binder, a third inorganic filler, and a third plasticizer;
and coating the third mixed slurry on the surface, back to the porous base layer, of the first inorganic fast ion conductor layer, and performing third drying treatment to enable the third mixed slurry to form the second organic fast ion conductor layer.
Optionally, the temperature range of the first drying treatment is 15-150 ℃, the temperature range of the second drying treatment is 15-200 ℃, and the temperature range of the third drying treatment is 15-150 ℃.
Another aspect of the present disclosure provides a battery cell comprising:
a positive electrode plate;
a negative pole piece; and
the separator of any one of the above-mentioned aspects, which is disposed between the positive electrode tab and the negative electrode tab.
Optionally, the second organic fast ion conductor layer of the separator faces the negative electrode plate, and the first organic fast ion conductor layer of the separator faces the positive electrode plate.
Another aspect of the present disclosure provides a battery including the battery cell of any one of the above-mentioned.
The technical scheme provided by the embodiment of the disclosure has at least the following beneficial effects:
through the cooperation of the first inorganic fast ion conductor layer and other film layers, the diaphragm is endowed with good mechanical strength, and the short circuit problem caused by the fact that the lithium dendrite of the negative pole piece penetrates through the diaphragm is avoided. Through setting up the fast ion conductor layer of first organic and the fast ion conductor layer of second organic, do benefit to and improve the compatibility between diaphragm and positive pole piece and the negative pole piece, reduce interface impedance, do benefit to and improve the charge speed of electric core and battery. And the ion conduction speeds of the first organic fast ion conductor layer, the second organic fast ion conductor layer and the first inorganic fast ion conductor layer are higher, so that the rapid charging of the battery core and the battery is facilitated.
Drawings
Fig. 1 is a schematic diagram illustrating a partial structure of a cell according to an exemplary embodiment of the present disclosure;
FIG. 2 illustrates a schematic structural view of a diaphragm shown in accordance with an exemplary embodiment of the present disclosure;
fig. 3 is a schematic diagram illustrating a partial structure of a cell according to an exemplary embodiment of the present disclosure;
FIG. 4 illustrates a flow chart of a method of manufacturing a diaphragm according to an exemplary embodiment of the present disclosure.
Detailed Description
Reference will now be made in detail to the exemplary embodiments, examples of which are illustrated in the accompanying drawings. When the following description refers to the accompanying drawings, like numbers in different drawings represent the same or similar elements unless otherwise indicated. The embodiments described in the following exemplary embodiments do not represent all embodiments consistent with the present disclosure. Rather, they are merely examples of apparatus and methods consistent with certain aspects of the present disclosure, as detailed in the appended claims.
The terminology used in the present disclosure is for the purpose of describing particular embodiments only and is not intended to be limiting of the disclosure. Unless otherwise defined, technical or scientific terms used herein shall have the ordinary meaning as understood by one of ordinary skill in the art to which this disclosure belongs. The use of "first," "second," and similar terms in the description and claims does not indicate any order, quantity, or importance, but rather is used to distinguish one element from another. Also, the use of the terms "a" or "an" and the like do not denote a limitation of quantity, but rather denote the presence of at least one. Unless otherwise indicated, the word "comprise" or "comprises", and the like, means that the element or item listed before "comprises" or "comprising" covers the element or item listed after "comprises" or "comprising" and its equivalents, and does not exclude other elements or items. The terms "connected" or "coupled" and the like are not restricted to physical or mechanical connections, but may include electrical connections, whether direct or indirect.
As used in this disclosure and the appended claims, the singular forms "a", "an", and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise. It should also be understood that the term "and/or" as used herein refers to and encompasses any and all possible combinations of one or more of the associated listed items.
In some embodiments, the cell includes a positive pole piece, a negative pole piece, and a separator disposed between the positive pole piece and the negative pole piece. The diaphragm includes: polyethylene base member, aluminium sesquioxide layer and polyvinylidene fluoride layer. The polyethylene substrate comprises a first surface and a second surface opposite to the first surface, the aluminum oxide layer is arranged on the first surface and faces the positive pole piece, and the polyvinylidene fluoride layer is arranged on the second surface and faces the negative pole piece. The diaphragm has good mechanical strength, and can prevent lithium dendrites formed on the negative pole piece from penetrating through the diaphragm to cause short circuit. However, the compatibility of the interface between the aluminum oxide and the positive electrode plate is poor, the interface impedance is high, and lithium ions can only diffuse through the gaps of the aluminum oxide particles, which is not favorable for the rapid charging of the battery. In addition, the polyvinylidene fluoride layer has low ion conduction speed and is not beneficial to the quick charging of the battery.
Based on the defects, the embodiment of the disclosure provides a diaphragm, a manufacturing method of the diaphragm, a battery core and a battery.
Some embodiments of the present disclosure provide for a battery for use in an electronic device, including but not limited to: the intelligent mobile phone comprises a mobile phone, a tablet computer, an iPad, a digital broadcast terminal, a messaging device, a game console, a medical device, a fitness device, a personal digital assistant, an intelligent wearable device, an intelligent television, a sweeping robot, an intelligent sound box and the like.
The battery includes a lithium ion battery, which may be a liquid lithium ion battery or a solid lithium ion battery.
Fig. 1 is a schematic diagram illustrating a partial structure of a battery cell 100 according to an exemplary embodiment of the present disclosure. The battery includes a cell, and referring to fig. 1, a cell 100 includes: the positive electrode plate 110, the negative electrode plate 120 and the diaphragm 130, wherein the diaphragm 130 is arranged between the positive electrode plate 110 and the negative electrode plate 120.
Illustratively, the positive electrode sheet 110 and the negative electrode sheet 120 are in a laminated winding structure, which is beneficial to increase the capacity of the battery cell 100.
Fig. 2 illustrates a schematic structural view of a diaphragm 130 according to an exemplary embodiment of the present disclosure. The separator 130 is used for the battery cell 100, and referring to fig. 2, the separator 130 includes: porous base layer 131, first organic fast ion conductor layer 132, first inorganic fast ion conductor layer 133 and second organic fast ion conductor layer 134. Porous base layer 131 includes a first side and a second side opposite the first side. The first organic fast ion conductor layer 132 is disposed on the first surface. The first inorganic fast ion conductor layer 133 is disposed on the second surface. The second organic fast ion conductor layer 134 is disposed on the first inorganic fast ion conductor layer 133 at the side opposite to the porous base layer 131.
Through the cooperation of the first inorganic fast ion conductor layer 133 and other film layers, a skeleton supporting function is provided for the separator 130, and the separator 130 is endowed with good mechanical strength, so that the problem of short circuit caused by the penetration of lithium dendrites of the negative electrode sheet 120 through the separator 130 is avoided. By arranging the first organic fast ion conductor layer 132 and the second organic fast ion conductor layer 134, the compatibility between the diaphragm 130 and the positive pole piece 110 and the negative pole piece 120 is improved, the interface impedance is reduced, and the charging speed of the battery cell 100 and the lithium ion battery is increased. Moreover, the ion conduction speeds of the first organic fast ion conductor layer 132, the second organic fast ion conductor layer 134 and the first inorganic fast ion conductor layer 133 are relatively fast, which is beneficial to fast charging of the battery cell 100 and the lithium ion battery.
In some embodiments, the surface of the first inorganic fast ion conductor layer 133 is provided with a plurality of grooves, and the second organic fast ion conductor layer 134 is connected with the plurality of grooves. Like this, increased the area of contact between first inorganic fast ion conductor layer 133 and the fast ion conductor layer 134 of second organic, increased interface compatibility between the two, reduced impedance, made better the integration between the interface between the two, do benefit to the quick conduction of lithium ion, and then do benefit to and promote electric core or lithium ion battery's the speed of charging. And the connecting strength between the first inorganic fast ion conductor layer 133 and the second organic fast ion conductor layer 134 can be improved.
In some embodiments, the separator 130 further comprises a second inorganic fast ion conductor layer disposed between the porous base layer 131 and the first organic fast ion conductor layer 132. In this way, the second inorganic fast ion conductor layer and the first inorganic fast ion conductor layer 133 cooperate to provide the separator 130 with good mechanical strength and ion fast conductivity. The materials of the first inorganic fast ion conductor layer 133 and the second inorganic fast ion conductor layer may be the same or different.
Fig. 3 is a schematic diagram illustrating a partial structure of a battery cell 100 according to an exemplary embodiment of the present disclosure. In some embodiments, referring to fig. 3, the second organic fast ion conductor layer 134 of the separator 130 faces the negative pole piece 120 and the first organic fast ion conductor layer 132 of the separator 130 faces the positive pole piece 110. In this way, the first inorganic fast ion conductor layer 133 is close to the negative electrode tab 120, which more effectively prevents the lithium dendrite formed on the negative electrode tab 120 from penetrating through the separator 130. Illustratively, when lithium dendrites grow on the negative electrode tab 120, this causes the lithium dendrites not to grow perpendicular to the separator 130 due to the barrier effect of the separator 130, and thus not to penetrate the separator 130.
The materials of the first organic fast ion conductor layer 132, the second organic fast ion conductor layer 134 and the first inorganic fast ion conductor layer 133 have a significant effect on the ion conductivity of the membrane 130, and the following examples are given for the three materials:
in some embodiments, the material of the first organic fast ion conductor layer 132 and the material of the second organic fast ion conductor layer 134 comprise an organic polymer electrolyte, such as a polymer comprising lone pair electron groups (-O-, C = O, C ≡ N). Illustratively, the material of the first organic fast ion conductor layer 132 and the material of the second organic fast ion conductor layer 134 each include at least one of polyethylene oxide and its derivatives, polysiloxane and its derivatives, polymethyl methacrylate and its derivatives, polyacrylate and its derivatives, polyvinyl alcohol and its derivatives, polyvinylidene fluoride and its derivatives, polyhexafluoropropylene and its derivatives, polyvinylidene fluoride-hexafluoropropylene and its derivatives, polyethylene glycol and its derivatives, polytetrafluoroethylene and its derivatives, polyacrylonitrile and its derivatives. The polyethylene oxide and the derivative thereof are two substances. The ion conductivity in the organic polymer electrolyte is better, which endows the first organic fast ion conductor layer 132 and the second organic fast ion conductor layer 134 with better ion conductivity, so that the battery cell 100 and the lithium ion battery can be charged quickly. In addition, the organic polymer electrolytes also have viscosity, so that the compatibility between the diaphragm 130 and the positive pole piece 110 is improved, and the interface impedance between the diaphragm 130 and the positive pole piece 110 and between the diaphragm 130 and the negative pole piece 120 is further reduced. Illustratively, the organic polymer electrolyte can enable lithium ions to conduct rapidly, thereby enabling the charging speed of the lithium ion battery to be increased.
The material of the first organic fast ion conductor layer 132 and the material of the second organic fast ion conductor layer 134 may be the same or different, and this disclosure does not limit this specifically.
In some embodiments, the materials of the first inorganic fast ion conductor layer 133 include: at least one of a layered lithium-based electrolyte, an oxide electrolyte, and a sulfide electrolyte. The materials of the first inorganic fast ion conductor layer 133 are fast ion conductor materials, and include defect structures, which form ion transmission paths, so that the ion transmission speed can be increased, the acquisition is easy, and the separator 130 has good mechanical strength.
In some embodiments, the material of the first inorganic fast ion conductor layer 133 includes a layered lithium-based electrolyte including lithium nitride (Li)3N). And/or the material of first inorganic fast ion conductor layer 133 comprises an oxide electrolyte comprising a crystalline inorganic electrolyte and a glassy inorganic electrolyte, wherein the glassy inorganic electrolyte comprises LiPON type and Li2O-B2O3-P2O5(including oxides of Li, B, and P after sintering), the oxide electrolyte includes: at least one of NASICON type, LISICON type, garnet type, perovskite type, and anti-perovskite type. And/or the material of the first inorganic fast ion conductor layer 133 includes a sulfide electrolyte, the sulfide electrolyte includes crystalline and glassy sulfide systems, the sulfide electrolyte includes: li10GeP2S12、Li10GeP2S12Derivatives of (5)、Li9.54Si1.74P1.44S11.7Cl0.3、Li9.54Si1.74P1.44S11.7Cl0.3Derivative of (5), Li7La3Zr2O12And Li7La3Zr2O12At least one of the derivatives of (1). These materials are advantageous for increasing the ion conduction speed, and the formed first inorganic fast ion conductor layer 133 has good mechanical strength, giving the separator 130 good mechanical properties.
In some embodiments, the material of porous base layer 131 comprises a polyolefin material. Illustratively, the material of the porous base layer 131 includes at least one of polyethylene and polypropylene.
The thickness of each film layer in the separator 130 can be adjusted according to actual needs. In some embodiments, the thickness of the first organic fast ion conductor layer 132 is in a range of 0.5-10 μm, such as 0.5 μm, 1 μm, 2 μm, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, or 10 μm. The thickness of the second organic fast ion conductor layer 134 is in the range of 0.5 to 10 μm, for example, 0.5 μm, 1 μm, 2 μm, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, or 10 μm. The thickness of the first inorganic fast ion conductor layer 133 is in the range of 0.5 to 10 μm, for example, 0.5 μm, 1 μm, 2 μm, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, or 10 μm. In this way, the first organic fast ion conductor layer 132, the second organic fast ion conductor layer 134, and the first inorganic fast ion conductor layer 133 are combined with the porous base layer 131, so that the separator 130 has good mechanical strength and fast ion conductivity.
FIG. 4 illustrates a flow chart of a method of manufacturing a diaphragm according to an exemplary embodiment of the present disclosure. Some embodiments of the present disclosure provide a manufacturing method applied to any one of the above-mentioned diaphragms, and referring to fig. 4, the manufacturing method includes:
and 41, forming a first organic fast ion conductor layer on the first surface of the porous base layer.
In some embodiments, step 41 comprises:
step 411, configuring a first mixed slurry comprising a first organic polymer electrolyte, a first additive and a first solvent, the first additive comprising: at least one of a first binder, a first inorganic filler, and a first plasticizer.
Illustratively, the first binder includes: at least one of polypropylene, polyethylene, sodium carboxymethylcellulose, polyvinylidene fluoride, polyethylene oxide, polysiloxane, polymethyl methacrylate, polyacrylates, polyvinyl alcohol, polyvinylidene fluoride, polyhexafluoropropylene, polyvinylidene fluoride-hexafluoropropylene, polyethylene glycol, polytetrafluoroethylene, polyacrylonitrile, and derivatives thereof. The first adhesive has viscosity and good ion conduction capability, and is beneficial to enabling a first organic fast ion conductor layer formed subsequently to have higher ion conduction speed.
Illustratively, the first inorganic filler includes at least one of alumina, titania, silica, and an inorganic fast ion conductor. Therefore, the first organic fast ion conductor layer formed subsequently has good mechanical strength.
Illustratively, the first solvent includes: at least one of acetonitrile, water, ethanol, isopropanol, methanol, N-methylpyrrolidone, isopropanol, N-butanol, and propanol.
Exemplarily, the first additive may be 0% to 50% by mass of the first mixed slurry.
Step 412, coating the first mixed slurry on the first surface, and performing a first drying process to form a first organic fast ion conductor layer from the first mixed slurry.
The temperature range of the first drying treatment is, for example, 15 to 150 ℃, and may be, for example, 15 ℃, 20 ℃, 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃ or 150 ℃. In this way, the first solvent can be evaporated, causing the first mixed paste to form the first organic fast ion conductor layer.
Step 42, forming a first inorganic fast ion conductor layer on the second surface of the porous base layer.
In some embodiments, step 42 comprises:
step 421, configuring a second mixed slurry comprising an inorganic solid electrolyte, a second additive and a second solvent, wherein the second additive comprises: at least one of a second binder, a second inorganic filler, and a second plasticizer.
Illustratively, the second binder includes: at least one of polypropylene, polyethylene, sodium carboxymethylcellulose, polyvinylidene fluoride, polyethylene oxide, polysiloxane, polymethyl methacrylate, polyacrylates, polyvinyl alcohol, polyvinylidene fluoride, polyhexafluoropropylene, polyvinylidene fluoride-hexafluoropropylene, polyethylene glycol, polytetrafluoroethylene, polyacrylonitrile, and derivatives thereof. The second adhesive has viscosity and good ion conduction capability, and is beneficial to enabling the first inorganic fast ion conductor layer formed subsequently to have higher ion conduction speed.
Illustratively, the second inorganic filler includes at least one of alumina, titania, silica, and an inorganic fast ion conductor. Therefore, the first organic fast ion conductor layer formed subsequently has good mechanical strength.
Illustratively, the second solvent includes: at least one of acetonitrile, water, ethanol, isopropanol, methanol, N-methylpyrrolidone, isopropanol, N-butanol, and propanol.
Exemplarily, the second additive may be 0% to 50% by mass of the second mixed slurry.
Step 422, coating the second mixed slurry on the second surface, and performing a second drying process to form the first inorganic fast ion conductor layer from the second mixed slurry.
The temperature range of the second drying treatment is, for example, 15 to 200 ℃, and may be, for example, 15 ℃, 20 ℃, 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃, 150 ℃, 160 ℃, 170 ℃, 180 ℃, 190 ℃ or 200 ℃. In this way, the second solvent may be evaporated, and the second mixed paste may form the first inorganic fast ion conductor layer.
And 43, forming a second organic fast ion conductor layer on the surface, opposite to the porous base layer, of the first inorganic fast ion conductor layer.
In some embodiments, step 43 comprises:
step 431, configuring a third mixed slurry comprising a second organic polymer electrolyte, a third additive and a third solvent, the third additive comprising: at least one of a third binder, a third inorganic filler, and a third plasticizer.
Illustratively, the third binder includes: at least one of polypropylene, polyethylene, sodium carboxymethylcellulose, polyvinylidene fluoride, polyethylene oxide, polysiloxane, polymethyl methacrylate, polyacrylates, polyvinyl alcohol, polyvinylidene fluoride, polyhexafluoropropylene, polyvinylidene fluoride-hexafluoropropylene, polyethylene glycol, polytetrafluoroethylene, polyacrylonitrile, and derivatives thereof. The third adhesive has viscosity and good ion conduction capability, and is beneficial to enabling a second organic fast ion conductor layer formed subsequently to have higher ion conduction speed.
Illustratively, the third inorganic filler includes at least one of alumina, titania, silica, and an inorganic fast ion conductor. Therefore, the second organic fast ion conductor layer formed subsequently has good mechanical strength.
Illustratively, the third solvent includes: at least one of acetonitrile, water, ethanol, isopropanol, methanol, N-methylpyrrolidone, isopropanol, N-butanol, and propanol.
Exemplarily, the third additive may be 0% to 50% by mass of the third mixed slurry.
And 432, coating the third mixed slurry on the surface, opposite to the porous base layer, of the first inorganic fast ion conductor layer, and performing third drying treatment to enable the third mixed slurry to form a second organic fast ion conductor layer.
The temperature range of the third drying treatment is, for example, 15 to 150 ℃, and may be, for example, 15 ℃, 20 ℃, 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃ or 150 ℃. In this way, the third solvent can be evaporated, and the third mixed paste can form the second organic fast ion conductor layer.
The manufacturing method of the diaphragm provided by the embodiment of the disclosure is simple, and in the manufactured diaphragm, the first inorganic fast ion conductor layer and other film layers are matched to give good mechanical strength to the diaphragm, so that the problem of short circuit caused by the fact that lithium dendrite of the negative pole piece penetrates through the diaphragm is avoided. Through setting up the fast ion conductor layer of first organic and the fast ion conductor layer of second organic, do benefit to and improve the compatibility between diaphragm and positive pole piece and the negative pole piece, reduce interface impedance, improve electric core and lithium ion battery's the speed of charging. And the ion conduction speeds of the first organic fast ion conductor layer, the second organic fast ion conductor layer and the first inorganic fast ion conductor layer are higher, so that the quick charging of the battery core and the lithium ion battery is facilitated.
The performance of the separator and lithium ion battery is further illustrated below in conjunction with more detailed examples:
example 1
The present embodiment provides a separator including: a polyethylene base layer having a thickness of 5 μm, a polyethylene oxide layer having a thickness of 1 μm provided on a first surface of the polyethylene base layer, and Li having a thickness of 1 μm provided on a second surface of the polyethylene base layer7La3Zr2O12Layer of Li7La3Zr2O12A polyethylene oxide layer with a surface and a thickness of 1 μm.
Example 2
The present embodiment provides a separator including: a polyethylene base layer having a thickness of 5 μm, a polymethyl methacrylate layer having a thickness of 1.5 μm provided on a first surface of the polyethylene base layer, and Li having a thickness of 1 μm provided on a second surface of the polyethylene base layer9.54Si1.74P1.44S11.7Cl0.3Layer of Li9.54Si1.74P1.44S11.7Cl0.3A layer of polyhexafluoropropylene having a surface and a thickness of 0.5 μm.
Example 3
The present embodiment provides a separator including: a polyethylene base layer having a thickness of 5 μm, a polyacrylonitrile layer having a thickness of 2 μm provided on a first surface of the polyethylene base layer, and Li having a thickness of 1 μm provided on a second surface of the polyethylene base layer10GeP2S12Layer of Li10GeP2S12A polyethylene glycol layer with a surface thickness of 1.2 μm.
Example 4
The present embodiment provides a separator including: a polypropylene base layer with the thickness of 5 microns, a polyethylene glycol layer with the thickness of 1 micron arranged on the first surface of the polypropylene base layer, a LiPON layer with the thickness of 0.55 microns arranged on the second surface of the polypropylene base layer, and a polyhexafluoropropylene layer with the thickness of 1.2 microns arranged on the surface of the LiPON layer.
Example 5
The present embodiment provides a separator including: a polypropylene base layer with a thickness of 5 μm, a LiPON layer with a thickness of 0.65 μm and arranged on a first surface of the polypropylene base layer, a polyethylene glycol layer with a thickness of 1 μm and arranged on the surface of the LiPON layer, a LiPON layer with a thickness of 0.55 μm and arranged on a second surface of the polypropylene base layer, and a polyhexafluoropropylene layer with a thickness of 1.2 μm and arranged on the surface of the LiPON layer.
Example 6
The present embodiment provides a separator including: a polypropylene base layer with a thickness of 5 μm, arranged on the first surface of the polypropylene base layerL having a thickness of 0.61 μm2iO-B2O3-P2O5Layer, is provided on L2iO-B2O3-P2O5A polyethylene glycol layer with the surface thickness of 1 μm, a LiPON layer with the thickness of 0.71 μm and arranged on the second surface of the polypropylene base layer, and a polyhexafluoropropylene layer with the thickness of 1.2 μm and arranged on the surface of the LiPON layer.
Comparative example
The present comparative example provides a separator comprising: a polyethylene base layer with the thickness of 5 mu m, an aluminum oxide layer with the thickness of 1.2 mu m arranged on the first surface of the polyethylene base layer, and a polyvinylidene fluoride layer with the thickness of 1 mu m arranged on the second surface of the polyethylene base layer.
Application examples
The mechanical strength of the diaphragms provided by the examples 1 to 6 and the comparative example are tested, and the mechanical strength of the diaphragms provided by the examples 1 to 6 is improved by 5 to 50 percent compared with that of the diaphragms provided by the comparative example.
The interface impedances between the diaphragm and the positive electrode piece and between the diaphragm and the negative electrode piece respectively provided in the embodiments 1 to 6 and the comparative example are detected, and the interface impedances between the diaphragm and the positive electrode piece and between the diaphragm and the negative electrode piece provided in the embodiments 1 to 6 are reduced by 5% to 80% compared with the interface impedances between the diaphragm and the positive electrode piece and between the diaphragm and the negative electrode piece provided in the comparative example.
Under the same conditions, the separators provided in examples 1 to 6 and the comparative example were manufactured into lithium ion batteries, and respectively numbered as a No. 1 lithium ion battery, a No. 2 lithium ion battery, a No. 3 lithium ion battery, a No. 4 lithium ion battery, a No. 5 lithium ion battery, a No. 6 lithium ion battery, and a comparative lithium ion battery in this order. Through detection, the charging speed of the No. 1 lithium ion battery, the No. 2 lithium ion battery, the No. 3 lithium ion battery, the No. 4 lithium ion battery, the No. 5 lithium ion battery and the No. 6 lithium ion battery is improved by 1% -10% compared with that of the comparative lithium ion battery.
In conclusion, the diaphragm provided by the embodiment of the disclosure has good mechanical strength, and the interface impedance between the diaphragm and the positive and negative electrode plates is small, which is beneficial to the quick charge of the lithium ion battery. In addition, the lithium ion battery adopting the diaphragm has higher charging speed.
For the method embodiments, since they substantially correspond to the apparatus embodiments, reference may be made to the apparatus embodiments for relevant portions of the description. The method embodiment and the device embodiment are complementary.
The above embodiments of the present disclosure may be complementary to each other without conflict.
The above description is only exemplary of the present disclosure and should not be taken as limiting the disclosure, as any modification, equivalent replacement, or improvement made within the spirit and principle of the present disclosure should be included in the scope of the present disclosure.

Claims (12)

1. A separator for a lithium ion battery, the separator comprising:
a porous substrate comprising a first side and a second side opposite the first side;
the first organic fast ion conductor layer is arranged on the first surface;
the first inorganic fast ion conductor layer is arranged on the second surface; and
the second organic fast ion conductor layer is arranged on one surface, back to the porous base layer, of the first inorganic fast ion conductor layer;
the material of the first inorganic fast ion conductor layer comprises a glassy inorganic electrolyte;
the surface of the first inorganic fast ion conductor layer is provided with a plurality of grooves, and the second organic fast ion conductor layer is connected with the grooves.
2. The separator of claim 1, wherein the material of the first organic fast ion conductor layer and the material of the second organic fast ion conductor layer each comprise at least one of polyethylene oxide and derivatives thereof, polysiloxane and derivatives thereof, polymethyl methacrylate and derivatives thereof, polyacrylate and derivatives thereof, polyvinyl alcohol and derivatives thereof, polyvinylidene fluoride and derivatives thereof, polyhexafluoropropylene and derivatives thereof, polyvinylidene fluoride-hexafluoropropylene and derivatives thereof, polyethylene glycol and derivatives thereof, polytetrafluoroethylene and derivatives thereof, polyacrylonitrile and derivatives thereof.
3. The separator of claim 1, wherein the glassy inorganic electrolyte comprises a LiPON type; and/or
The material of the first inorganic fast ion conductor layer further comprises a layered lithium-based electrolyte, and the layered lithium-based electrolyte comprises lithium nitride; and/or
The material of the first inorganic fast ion conductor layer further comprises an oxide electrolyte comprising: at least one of NASICON type, LISICON type, garnet type, perovskite type, and anti-perovskite type; and/or
The material of the first inorganic fast ion conductor layer further comprises a sulfide electrolyte comprising: li10GeP2S12、Li10GeP2S12Derivative of (5), Li9.54Si1.74P1.44S11.7Cl0.3、Li9.54Si1.74P1.44S11.7Cl0.3Derivative of (5), Li7La3Zr2O12And Li7La3Zr2O12At least one of the derivatives of (1).
4. The separator of claim 1 wherein the first organic fast ion conductor layer has a thickness in the range of 0.5 to 10 μm, the second organic fast ion conductor layer has a thickness in the range of 0.5 to 10 μm, and the first inorganic fast ion conductor layer has a thickness in the range of 0.5 to 10 μm.
5. A method for manufacturing a separator, which is applied to the separator according to any one of claims 1 to 4, comprising:
forming a first organic fast ion conductor layer on the first surface of the porous base layer;
forming a first inorganic fast ion conductor layer on the second surface of the porous base layer;
and forming a second organic fast ion conductor layer on one surface of the first inorganic fast ion conductor layer, which faces away from the porous base layer.
6. The method of manufacturing according to claim 5, wherein forming a first organic fast ion conductor layer on the first side of the porous base layer comprises:
configuring a first mixed slurry comprising a first organic polymer electrolyte, a first additive, and a first solvent, the first additive comprising: at least one of a first binder, a first inorganic filler, and a first plasticizer;
and coating the first mixed slurry on the first surface, and performing first drying treatment to enable the first mixed slurry to form the first organic fast ion conductor layer.
7. The method of manufacturing according to claim 6, wherein the forming a first inorganic fast ion conductor layer on the second side of the porous base layer comprises:
configuring a second mixed slurry comprising an inorganic solid state electrolyte, a second additive, and a second solvent, the second additive comprising: at least one of a second binder, a second inorganic filler, and a second plasticizer;
and coating the second mixed slurry on the second surface, and performing second drying treatment to enable the second mixed slurry to form the first inorganic fast ion conductor layer.
8. The method of manufacturing according to claim 7, wherein forming a second organic fast ion conductor layer on a side of the first inorganic fast ion conductor layer opposite to the porous base layer comprises:
configuring a third mixed slurry comprising a second organic polymer electrolyte, a third additive, and a third solvent, the third additive comprising: at least one of a third binder, a third inorganic filler, and a third plasticizer;
and coating the third mixed slurry on the surface, back to the porous base layer, of the first inorganic fast ion conductor layer, and performing third drying treatment to enable the third mixed slurry to form the second organic fast ion conductor layer.
9. The method according to claim 8, wherein the temperature of the first drying treatment is in a range of 15 to 150 ℃, the temperature of the second drying treatment is in a range of 15 to 200 ℃, and the temperature of the third drying treatment is in a range of 15 to 150 ℃.
10. A battery cell, comprising:
a positive electrode plate;
a negative pole piece; and
the separator according to any one of claims 1 to 4, which is provided between the positive electrode sheet and the negative electrode sheet.
11. The electrical core of claim 10, wherein the second organic fast ion conductor layer of the separator faces the negative electrode sheet, and the first organic fast ion conductor layer of the separator faces the positive electrode sheet.
12. A battery comprising the cell of claim 10 or 11.
CN202010465971.9A 2020-05-28 2020-05-28 Diaphragm and manufacturing method thereof, battery core and battery Pending CN111384346A (en)

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