CN116345064A - Preparation method of functional battery diaphragm - Google Patents

Preparation method of functional battery diaphragm Download PDF

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Publication number
CN116345064A
CN116345064A CN202211723621.3A CN202211723621A CN116345064A CN 116345064 A CN116345064 A CN 116345064A CN 202211723621 A CN202211723621 A CN 202211723621A CN 116345064 A CN116345064 A CN 116345064A
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Prior art keywords
diaphragm
battery
gel
functional
cellulose
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CN202211723621.3A
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徐桂银
朱小青
张佳
赵红英
崔国士
朱美芳
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Donghua University
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Donghua University
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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
    • H01M50/44—Fibrous 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
    • H01M50/403—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
    • H01M50/431—Inorganic material
    • H01M50/434—Ceramics
    • 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
    • H01M50/457—Separators, membranes or diaphragms characterised by the material having a layered structure comprising three or more layers
    • 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

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

Abstract

The invention relates to a preparation method of a functional battery diaphragm. The preparation method comprises the following steps: adding the nano cellulose gel into water, performing ultrasonic dispersion to obtain nano cellulose dispersion liquid, and then mixing the nano cellulose dispersion liquid with ceramic slurry to obtain a coating liquid containing cellulose gel; the PE diaphragm is laid on a glass plate, a coating liquid containing cellulose gel is coated on at least one surface of the PE diaphragm, and the PE diaphragm is dried. The functional battery diaphragm prepared by the method has excellent mechanical properties, high temperature resistance, degradability, excellent mechanical strength and good affinity with lithium ions.

Description

Preparation method of functional battery diaphragm
Technical Field
The invention belongs to the field of battery energy storage materials, and particularly relates to a preparation method of a functional battery diaphragm.
Background
Carbon neutralization has become an important development goal worldwide, and electrochemical storage technology is widely recognized as a promising approach to achieve it. In recent years, research on lithium ion batteries has been focused, and rechargeable Lithium Ion Batteries (LIBs) have been commercialized in the 90 th century of 20 th century, and have been powering most consumer electronics and electric automobiles due to their high energy density, long cycle life, and the like. However, the slow reaction kinetics and fast dendrite growth are headache issues that can compromise the practical performance of metal-based batteries. In particular, uncontrolled dendrite growth can greatly disrupt the negative electrode-electrolyte interface, even penetrating the separator, leading to failure of the cell performance. To date, various methods have been used to inhibit dendrite formation and protect the negative electrode from corrosion, such as interface modification, by introducing conductive materials or interface layers, electrolyte additives coordinate the electrolyte environment, homogenize the interface electric field, induce uniform deposition of metal ions. However, the implementation of these measures is relatively complex and Gao Angjia grid of electrolyte additives limits its widespread use. To address these issues, developing a battery separator that simultaneously promotes ion transport and homogenization has become a challenge in developing high performance energy storage devices.
The battery separator is an important component of the battery, has great influence on the performance of the battery, and is particularly important for obtaining a lithium ion battery with high cycle performance. The separator is placed between two electrodes, should have high ionic conductivity, good mechanical and thermal stability, and can be divided into six main types: microporous films, nonwoven films, electrospun films, exterior surface modified films, composite films, and polymer blends. The separator can prevent physical contact between the electrodes and allow transfer of ions, while hardly affecting the electrochemical performance of the battery in conventional porous separators (glass fiber, filter paper and polypropylene). Inspired by membrane discovery in LIBs and Li-S cells, functionalized membranes can optimize cell performance by modulating ion diffusion, selective ion screening functions, generating uniform electric fields, and the like. In recent years, fiber membranes prepared by electrospinning technology are helpful to promote uniform distribution of electric fields on electrode surfaces due to their high porosity, excellent ion mobility and multifunctionality. The electrospun fiber diaphragm prepared by the technology can absorb a large amount of electrolyte and has higher ionic conductivity, so that the electrospun fiber diaphragm has good electrochemical performance. Wang (Yang Wang, long forming Zhang, tianxi Liu et al thermo-mechanical separator of cross-linked polyimide fibers with narrowed pore size for lithium-ion batteries [ J ]. J Membrane Sci.2022; 121004.) et al report a viable, scalable process for preparing heat resistant films of crosslinked PI fibers (c-PI) having an adhesion structure between adjacent fibers by electrospinning of polyamino acid (PAA) and Polystyrene (PS). The resulting c-PI film had a thickness of 0.78 μm and high thermal stability, and did not shrink at 250 ℃. Thereby effectively inhibiting the formation and growth of lithium dendrites. Therefore, the lithium ion battery with the cross-linked PI fiber diaphragm has higher specific capacity and good cycle durability.
Disclosure of Invention
The invention aims to solve the technical problem of providing a preparation method of a functional battery diaphragm, so as to solve the problems of poor hydrophilicity of most commercial diaphragms to water-based electrolytes and dendrite formation in the battery charging and discharging process at present.
The invention provides a functional battery diaphragm, which takes a PE diaphragm as a matrix, and coats a nano cellulose fiber layer on at least one side surface of the PE diaphragm, wherein the nano cellulose fiber layer comprises nano cellulose and Al 2 O 3 。
Preferably, the nanocellulose comprises cellulose nanocrystalline NCC and/or cellulose nanofiber NCF.
Preferably, the PE membrane is a commercial PE membrane.
The invention also provides a preparation method of the functional battery diaphragm, which comprises the following steps:
(1) Adding the nano cellulose gel into water, and performing ultrasonic dispersion to obtain nano cellulose dispersion liquid;
(2) Dispersing the nanocellulose in the step (1)Mixing with ceramic slurry to obtain coating liquid containing cellulose gel, wherein the ceramic slurry contains Al 2 O 3 ；
(3) And (3) spreading the PE diaphragm on a glass plate, coating the coating liquid containing cellulose gel in the step (2) on at least one surface of the PE diaphragm, and drying to obtain the functional battery diaphragm.
Preferably, the mass fraction of nanocellulose in the nanocellulose gel in step (1) is 0.5 to 5wt%, more preferably 1 to 3wt%.
Preferably, the weight ratio of the nanocellulose gel to the water in the step (1) is 5:95-20:80.
Preferably, al is contained in the ceramic slurry in the step (2) 2 O 3 The mass fraction is 20-80 wt%, more preferably 30-50 wt%.
Preferably, the mass fraction of the nanocellulose gel in the coating liquid containing the cellulose gel in the step (2) is 1-3 wt%.
Preferably, al in the step (2) 2 O 3 Comprising alpha-Al 2 O 3 、β-Al 2 O 3 、γ-Al 2 O 3 At least one of them.
Preferably, the thickness of the PE diaphragm in the step (3) is 5-9 μm; the drying time is 2-10 hours, and the drying temperature is 40-80 ℃.
Preferably, the thickness of the functional battery separator in the step (3) is 10-30 μm.
The invention also provides application of the functional battery diaphragm in a metal-based battery.
Preferably, the metal-based battery comprises at least one of an aqueous zinc ion battery, an aqueous lithium ion battery, a zinc ion battery, a lithium ion battery, and an aqueous sodium ion battery.
Advantageous effects
The functional battery diaphragm has excellent mechanical property, high temperature resistance, degradability, excellent mechanical strength and good affinity with lithium ions, such as composite diaphragm PE/Al 2 O 3 Tensile strain of/NCC of 122%, tensile strength up to 77.4MPa, and PE/Al composite diaphragm 2 O 3 The tensile strain of the NCF is 111.6 percent, the tensile strength is up to 72.4MPa, and the PE/Al ratio is high 2 O 3 The contact angle of the NCC composite diaphragm is 42.8-56.3 degrees, PE/Al 2 O 3 The contact angle of the NCF composite membrane is 56.3 degrees, and the contact angle of the PE membrane is 104.2 degrees, which shows that the hydrophilicity of the composite membrane after being coated with cellulose is greatly improved.
Drawings
Fig. 1 is a graph showing mechanical stretching of the composite separator according to example 1 or example 2.
Fig. 2 is a graph of contact angle measurements of samples of example 1, example 2 and comparative example.
Fig. 3 is a time-voltage curve of a Li// Li symmetric battery assembled from the functional composite separator prepared in example 1.
Fig. 4 is a graph of cyclic charge-discharge specific capacity data of a Li// S battery assembled with the functional composite separator prepared in example 1.
Fig. 5 is a time-voltage curve of a Li// Li symmetric battery assembled from the functional composite separator prepared in example 2.
Fig. 6 is a graph of cyclic charge-discharge specific capacity data of a Li// S battery assembled with the functional composite separator prepared in example 2.
Fig. 7 is a time-voltage curve of a Li// Li symmetric battery assembled with the separator of comparative example 1.
Detailed Description
The invention will be further illustrated with reference to specific examples. It is to be understood that these examples are illustrative of the present invention and are not intended to limit the scope of the present invention. Further, it is understood that various changes and modifications may be made by those skilled in the art after reading the teachings of the present invention, and such equivalents are intended to fall within the scope of the claims appended hereto.
Example 1
The embodiment prepares a functional battery diaphragm, and the preparation method specifically comprises the following steps:
(1) 5g of nanocellulose (NCC, 2%) gel was placed in a 100ml beaker, 45g of deionized water was added, and the nanocellulose dispersion was obtained by ultrasonic dispersion.
(2) A certain amount of the cellulose dispersion and the ceramic slurry (Al) were then removed by a pipette 2 O 3 40%) are fully and uniformly mixed to obtain the coating liquid with the cellulose gel content of 2%.
(3) Spreading 7 μm PE membrane on glass plate, uniformly coating the coating liquid on the surfaces of two sides of the membrane by using a coating tester, and drying to obtain PE/Al 2 O 3 The NCC composite membrane has a thickness of 15 μm.
Composite separator PE/Al as shown in FIG. 1 2 O 3 The tensile strain of the NCC is 122 percent, the tensile strength is up to 77.4MPa, and the composite diaphragm PE/Al 2 O 3 The tensile strain of the NCF was 111.6%, and the tensile strength was as high as 72.4MPa, as shown in FIG. 2, PE/Al 2 O 3 The contact angle of the NCC composite diaphragm is 42.8-56.3 degrees, PE/Al 2 O 3 The contact angle of the NCF composite membrane is 56.3 degrees, and the contact angle of the PE membrane is 104.2 degrees, which shows that the hydrophilicity of the composite membrane after being coated with cellulose is greatly improved.
PE/Al prepared in example 1 2 O 3 The NCC composite diaphragm is assembled into a Li// Li symmetrical battery, and the steps are as follows:
(1) The negative electrode was a lithium sheet having a diameter of 10 mm.
(2) LITFSI with electrolyte of 1M is dissolved in DME/DOL solvent with equal volume configuration, and 2% LiNO is added 3 The amount of electrolyte used was 60. Mu.L. The membrane used was the membrane sheet obtained in example 1. The lithium sheet, the electrolyte and the diaphragm sheet were assembled into a CR2025 coin cell.
(3) Test conditions: at 0.25mA cm -2 And (3) performing charge and discharge tests under the current density condition. The electrochemical charge-discharge curve of the symmetrical cell is shown in fig. 3. From the test curves, it was found that, at a constant current density, the polarization voltage reached 13mV,
the functional composite separator prepared in example 1 was assembled into a lithium sulfur battery, and the procedure was as follows:
(1) The negative electrode was a lithium sheet with a diameter of 16 mm.
(2) The use ofLITFSI with electrolyte of 1M is dissolved in DME/DOL solvent with equal volume configuration, and 2% LiNO is added as additive 3 The amount of electrolyte used was 20. Mu.L. The membrane used was the membrane sheet obtained in example 1.
(3) The anode material is selected from sulfur-carbon powder, and the slurry is prepared by dissolving sulfur powder, conductive carbon black and polyvinylidene fluoride binder in N-methyl pyrrolidone according to the weight ratio of 7:2:1; the positive electrode slurry was then coated onto aluminum foil using a 200 μm doctor blade and dried in a forced air oven at 50 ℃ for 10 hours; cutting the positive electrode plate into a positive electrode plate with the diameter of 10mm after the solvent is volatilized completely.
(4) And assembling the positive plate, the negative plate, the electrolyte and the diaphragm into the CR2025 button battery in a glove box.
The battery cycle test uses a blue-powered CT3002A test platform, and the charge-discharge voltage range is 1.7-2.8V.
Test conditions:
the sulfur positive electrode in the secondary battery had a load of 1.5mg cm -2 The charge and discharge process was set at 0.2C (1c=1675ma g -1 ) And (3) performing charge and discharge tests on the multiplying power of the battery. The electrochemical charge-discharge curve of the secondary lithium sulfur battery is shown in fig. 4. The specific capacity of the constituent battery of the aqueous composite separator prepared in example 1 reached 915.6mAh g at 0.2C -1 While its discharge plateau is higher. The result proves that the secondary lithium-sulfur battery based on the water-based composite diaphragm has better electrochemical charge-discharge performance.
Example 2
(1) 5g of nanocellulose (NCF, 2%) gel was placed in a 100ml beaker, 45g of deionized water was added, and the nanocellulose dispersion was obtained by ultrasonic dispersion.
(2) A certain amount of the cellulose dispersion and the ceramic slurry (Al) were then removed by a pipette 2 O 3 40%) are fully and uniformly mixed to obtain the coating liquid with the cellulose gel content of 2%.
(3) Spreading 7 μm PE membrane on glass plate, uniformly coating the coating liquid on the surfaces of two sides of the membrane by using a coating tester, and drying to obtain PE/Al 2 O 3 NCF composite membrane, thicknessThe degree was 15. Mu.m.
Functional PE/Al prepared in example 2 2 O 3 the/NCF composite diaphragm is assembled into a Li// Li symmetrical battery, and the steps are as follows:
(3) The negative electrode was a lithium sheet with a diameter of 8 mm.
(4) LITFSI with electrolyte of 1M is dissolved in DME/DOL solvent with equal volume configuration, and 2% LiNO is added 3 The amount of electrolyte used was 60. Mu.L. The membrane used was the membrane sheet obtained in example two. The lithium sheet, the electrolyte and the diaphragm sheet were assembled into a CR2025 coin cell.
(3) Test conditions: at 0.25mA cm -2 And (3) performing charge and discharge tests under the current density condition. The electrochemical charge-discharge curve of the symmetrical cell is shown in fig. 5. It is known from the test curve that at a constant current density, the polarization voltage reaches only 10mV, and the time-voltage curve does not have a fluctuation phenomenon.
Functional PE/Al prepared in example 2 2 O 3 The NCF composite diaphragm is assembled into a lithium sulfur battery, and the steps are as follows:
(5) The negative electrode was a lithium sheet with a diameter of 16 mm.
(6) LITFSI with electrolyte of 1M is dissolved in DME/DOL solvent with equal volume configuration, and 2% LiNO is added 3 The amount of electrolyte used was 10. Mu.L. The membrane used was the functional composite membrane sheet obtained in example 2.
(7) The anode material is selected from sulfur-carbon powder, and the slurry is prepared by dissolving sulfur powder, conductive carbon black and polyvinylidene fluoride binder in N-methyl pyrrolidone according to the weight ratio of 7:2:1; the positive electrode slurry was then coated onto aluminum foil using a 200 μm doctor blade and dried in a forced air oven at 50 ℃ for 10 hours; cutting the positive electrode plate into a positive electrode plate with the diameter of 10mm after the solvent is volatilized completely.
(8) And assembling the positive plate, the negative plate, the electrolyte and the diaphragm into the CR2025 button battery in a glove box.
The battery cycle test uses a blue-powered CT3002A test platform, and the charge-discharge voltage range is 1.7-2.8V.
Test conditions:
the sulfur positive electrode in the secondary battery had a load of 1.5mg cm -2 The charge and discharge process was set at 0.2C (1c=1675ma g s -1 ) And (3) performing charge and discharge tests on the multiplying power of the battery. The electrochemical charge and discharge curves of the lithium sulfur secondary battery are shown in fig. 6. Under the condition of 0.2C, the specific capacity reaches 973.3mAh g s -1 While its coulomb efficiency remains around 99%. The result shows that the secondary lithium sulfur battery based on the diaphragm with the surface functional group carboxyl has excellent electrochemical charge and discharge performance.
Comparative example 1
The Li// Li symmetric battery was assembled from uncoated polyethylene separators as follows:
(1) The lithium pieces were cut into 8mm diameter discs.
(2) An electrolyte: LITFSI, 1M, was dissolved in an equal volume of DME/DOL solvent and the amount of electrolyte used was 50. Mu.L. The separator used was an uncoated polyethylene separator. The zinc sheet, electrolyte and separator sheet were assembled into a CR2025 coin cell.
(3) Test conditions: at 0.25mA cm -2 And (3) performing charge and discharge tests under the current density condition. The electrochemical charge-discharge curve of the symmetrical cell is shown in fig. 7. According to the test curve, the time-voltage curve of the Li// Li symmetrical battery shows that the polarization voltage reaches 24mV at a constant current density and the curve has certain fluctuation in a test interval of 100 hours. As can be seen from FIG. 7 in comparison with FIG. 3 and FIG. 5, the PE/Al is used under the same test conditions 2 O 3 NCC and PE/Al 2 O 3 The test result of the NCF membrane has smaller polarization voltage, and the time-voltage curve is more stable, which shows that the membrane coated by the nanocellulose improves the cycle stability of the battery.

Claims (10)

1. A functional battery diaphragm is characterized in that a PE diaphragm is taken as a matrix, at least one side surface of the PE diaphragm is coated with a nano cellulose fiber layer, and the nano cellulose fiber layer comprises nano cellulose and Al 2 O 3 。
2. The functional battery separator of claim 1, wherein the nanocellulose comprises cellulose nanocrystalline NCC and/or cellulose nanofiber NCF.
3. A method of making a functional battery separator comprising:
(1) Adding the nano cellulose gel into water, and performing ultrasonic dispersion to obtain nano cellulose dispersion liquid;
(2) Mixing the nanocellulose dispersion in step (1) with a ceramic slurry to obtain a coating solution containing cellulose gel, wherein the ceramic slurry contains Al 2 O 3 ；
(3) And (3) spreading the PE diaphragm on a glass plate, coating the coating liquid containing cellulose gel in the step (2) on at least one surface of the PE diaphragm, and drying to obtain the functional battery diaphragm.
4. The preparation method according to claim 1, wherein the mass fraction of the nanocellulose in the nanocellulose gel in step (1) is 0.5-5 wt%; the weight ratio of the nano cellulose gel to the water is 5:95-20:80.
5. The method according to claim 1, wherein Al in the ceramic slurry in the step (2) 2 O 3 The mass fraction of (2) is 20-80 wt%.
6. The method according to claim 1, wherein the mass fraction of the nanocellulose gel in the coating liquid containing the cellulose gel in the step (2) is 1-3 wt%.
7. The method according to claim 1, wherein Al in the step (2) 2 O 3 Comprising alpha-Al 2 O 3 、β-Al 2 O 3 、γ-Al 2 O 3 At least one of them.
8. The method according to claim 1, wherein the PE separator in the step (3) has a thickness of 5 to 9 μm; the drying time is 2-10 hours, and the drying temperature is 40-80 ℃.
9. Use of the functional battery separator of claim 1 in a metal-based battery.
10. The use of claim 9, wherein the metal-based battery comprises at least one of an aqueous zinc ion battery, an aqueous lithium ion battery, a zinc ion battery, a lithium ion battery, and an aqueous sodium ion battery.
CN202211723621.3A 2022-12-30 2022-12-30 Preparation method of functional battery diaphragm Pending CN116345064A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117254209A (en) * 2023-11-17 2023-12-19 江苏中兴派能电池有限公司 Composite battery diaphragm and preparation method and application thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117254209A (en) * 2023-11-17 2023-12-19 江苏中兴派能电池有限公司 Composite battery diaphragm and preparation method and application thereof
CN117254209B (en) * 2023-11-17 2024-01-30 江苏中兴派能电池有限公司 Composite battery diaphragm and preparation method and application thereof

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