CN115133222A - Double-coating diaphragm capable of simultaneously inhibiting lithium dendrite and transition metal dissolution, preparation method and lithium metal battery applying diaphragm - Google Patents
Double-coating diaphragm capable of simultaneously inhibiting lithium dendrite and transition metal dissolution, preparation method and lithium metal battery applying diaphragm Download PDFInfo
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- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 claims description 2
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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
- H01M50/449—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
-
- 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
-
- 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
- H01M50/431—Inorganic material
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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
- H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
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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
- H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
-
- 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
- H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
- H01M50/497—Ionic conductivity
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- Chemical Kinetics & Catalysis (AREA)
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- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Cell Separators (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to a double-coating diaphragm for simultaneously inhibiting lithium dendrite and transition metal dissolution, a preparation method and a lithium metal battery applying the diaphragm. The coating on the side of the diaphragm opposite to the negative electrode contains polymer binder and inorganic substances which can react with lithium chemically and alloy. The coating on the side, opposite to the positive electrode, of the diaphragm prepared by the method can adsorb moisture in the electrolyte of the battery, so that the generation of hydrofluoric acid is reduced, and the dissolution of transition metal of the positive electrode is slowed down; the coating on the side opposite to the negative electrode is contacted with the lithium negative electrode in an electrolyte environment and stands for a period of time, inorganic matters in the coating can react with lithium in situ and are finally converted into lithium-containing alloy and lithium-containing inorganic matters, and the lithium-containing inorganic matters are used as an interface layer between negative electrode diaphragms in a circulating process to reduce interface impedance, accelerate lithium ion transmission and reduce generation of dendritic crystals. Through the excellent performance of each of the two coatings, the capacity retention rate and the cycle life of the battery are improved in a double-pipe manner.
Description
Technical Field
The invention belongs to the technical field of lithium metal battery diaphragms, and relates to a double-coating diaphragm capable of simultaneously inhibiting lithium dendrite and transition metal dissolution, a preparation method of the double-coating diaphragm and a lithium metal battery applying the diaphragm.
Background
A new round of scientific and technological revolution around the world promotes the industrial layout of lithium ion batteries in portable electronic equipment, and gradually develops vigorously in emerging fields such as traffic power supplies, energy storage base stations, aerospace military industry and the like. At present, LiCoO is traditionally used 2 、LiFePO 4 The energy density of commercial batteries with graphite as the negative electrode as the positive electrode is close to the theoretical limit, and the demand of the market on energy type energy storage systems is difficult to meet. But will have an ultra-high theoretical specific capacity (3860mA h g) -1 ) Low electrochemical potential (-3.04Vvs standard hydrogen electrode) and low density (0.53g cm) -3 ) Matching of a lithium metal negative electrode with a high voltage positive electrode (transition metal oxide) is considered a necessary option to improve overall battery capacity and energy density.
However, in commercial electrolytes, the instability of the positive and negative electrode interfaces has limited the development of such batteries. The current electrochemical window meeting the positive electrode requirements is based on lithium hexafluorophosphate (LiPF) 6 ) Carbonate-based electrolyte system of lithium salt, but LiPF 6 For water content (H) 2 O) is sensitive and is easy to react to generate hydrofluoric acid (H)F) HF can corrode the anode material to dissolve out transition metal ions Ni, Co and Mn, and the structural stability of the material is damaged, so that the cycle performance of the battery is rapidly attenuated. The main method of modification is to construct a coating layer on the surface of the anode particles to isolate the contact of the electrolyte and the anode material, or introduce an electrolyte additive to capture H in the electrolyte 2 However, the introduction of the coating layer generally increases the interface resistance, and the electrolyte additive is difficult to maintain at the positive and negative electrode interfaces and is chemically stable, and is continuously consumed along with the oxidation reduction.
At the negative electrode interface, since lithium metal is very active, in the battery environment, lithium metal will react with the liquid electrolyte aprotic solvent and form a solid electrolyte interface film (SEI). During repeated lithium plating/stripping, the non-uniform deposition of lithium tends to crack the brittle SEI, eventually leading to continued consumption of lithium in the positive electrode and electrolyte and a shortened battery cycle life. At present, common methods for improving SEI films are as follows: constructing an artificial protective layer and introducing an electrolyte film-forming additive. However, artificially created ex-situ protective layers tend to have weaker interfacial adhesion than in-situ generated SEI, resulting in discontinuous ion transport at the protective layer/negative electrode interface. While SEI components derived from electrolyte film-forming additives generally increase in resistance under high rate or low temperature cycling conditions, limiting high power output of the battery. Therefore, on the other hand, achieving uniform lithium deposition behavior is considered as an essential requirement to obtain stable SEI. The remarkable effect of anchoring "lithium-philic" seeds (e.g., Ag, Au, and Zn) selected for alloying with lithium onto a deposition substrate for inducing uniform deposition of lithium is currently demonstrated by a number of reports. In order to avoid volume expansion of alloy particles and serious irreversible lithium consumption in the initial alloying process, the direct application of the lithium-rich alloy as the negative electrode protective layer is considered to be an important way for realizing uniform lithium deposition and constructing a fast ion conduction negative electrode protective layer at the same time. Research finds that the lithium-rich alloy has strong adhesion with lithium metal and rapid ion transport capability, and is used for insulating inorganic lithium-conducting compounds (LiI and Li) 2 S, LiF) act synergistically to function primarily as ionic conduction. However, harsh preparation processes (high temperature, chemical pretreatment) and moisture-proof, inert gasesThe storage conditions greatly impair the superiority of the strategy, resulting in inefficient production processes that are not easily controlled.
The diaphragm is a key material which can be in close contact with the positive electrode and the negative electrode, and is stable in air. Whereas surface coating is a common strategy to alter the separator physicochemical properties such as ionic conductivity, lithium transference number, porosity and electrolyte wettability. If the interfacial behavior of the electrode can be tuned by building multifunctional coatings on the separator, complex electrode modifications can be achieved by simple separator modifications.
Disclosure of Invention
Technical problem to be solved
In order to avoid the defects of the prior art, the invention provides a double-coating diaphragm capable of simultaneously inhibiting lithium dendrite and transition metal dissolution, a preparation method and a lithium metal battery applying the diaphragm. In the battery, the coating on the side of the diaphragm opposite to the positive electrode can capture the moisture in the electrolyte, reduce the generation of HF and inhibit the dissolution of transition metal; the coating on the side, opposite to the negative electrode, of the diaphragm is in contact with the lithium negative electrode and stands still, then in-situ reaction is carried out to generate a lithium-rich alloy layer and a lithium-conducting inorganic compound, and the lithium-rich alloy layer and the lithium-conducting inorganic compound are used as an interface layer between the negative electrode diaphragms in the circulation process to reduce interface impedance, accelerate lithium ion transmission and reduce dendritic crystal growth. Finally, the two coatings improve the capacity retention rate and the cycle life of the battery together in a double pipe manner.
Technical scheme
A double-coating diaphragm for simultaneously inhibiting lithium dendrite and transition metal dissolution is characterized by comprising a base film and coatings attached to two sides of the base film, wherein the coatings are respectively opposite to a positive electrode or a negative electrode; the coating comprises a polymer binder and functional materials in a mass ratio of 1: 2-20, wherein: the functional material in the coating layer at the side opposite to the positive electrode is a moisture absorbable material, and H can be stored 2 A porous inorganic material of O molecules; the functional material in the coating layer on the side opposite to the negative electrode is an inorganic substance capable of chemically and alloy reacting with lithium, namely a non-lithium element in the lithium-rich alloy and a non-metal element capable of forming a stable inorganic compound with lithium.
The mass ratio of the polymer binder to the functional material is 1: (2-20) (the effect of the coating is affected by the content of the polymer binder being too high, and if the content is too low, the adhesion is insufficient and the coating is liable to fall off).
Preferably, the functional material of the coating layer on the side of the membrane facing the positive electrode is a moisture absorbable material, in particular a storable H 2 A porous material of O molecules. For example: porous SiO 2 One or a combination of several of MOF and molecular sieve.
Preferably, the functional material of the coating on the side of the separator facing the negative electrode is an inorganic substance capable of chemically and alloy reacting with lithium, and specifically consists of non-lithium elements in the lithium-rich alloy and non-metal elements capable of forming stable inorganic compounds with lithium. For example: AgSe, InF 2 、SnS 2 、SnCl 2 、SbF 2 、AlF 3 One or a combination of more of ZnS, ZnSe, MgS and MgSe. The chemical reaction and the alloy reaction with lithium can be realized by means of in-situ reaction and conversion into lithium-containing alloy and lithium-containing inorganic substances after the coating is contacted and stood with a lithium cathode in an electrolyte environment.
The base film is a ceramic base film, a polyethylene PE base film, a polypropylene PP base film, a polypropylene/polyethylene/polypropylene multi-layer base film, a polyethylene glycol terephthalate (PET) base film, a Polyacrylonitrile (PAN) base film, a glass fiber base film, a cellulose base film or a polyvinylidene fluoride (PVDF) base film.
The polymer binder is: the weight-average molecular weight of the composite material is 5-300 ten thousand by one or a combination of more of sodium carboxymethylcellulose (CMC), styrene butadiene latex (SBR), polyvinylidene fluoride (PVDF), poly (vinylidene fluoride-hexafluoropropylene) PVDF-HFP, polyethylene oxide (PEO), polyacrylic acid (PAA) or polyvinylpyrrolidone (PVP).
The thickness of the coating on the side of the diaphragm opposite to the anode is 0.1-5 mu m, and the thickness of the coating on the side of the diaphragm opposite to the cathode is 0.2-15 mu m.
Preferably, the thickness of the coating on the side of the diaphragm opposite to the positive electrode is 0.1-5 mu m (if the coating is too thick, the mass of the diaphragm is increased, the energy density of the battery is not favorably improved, and if the thickness is too low, the H in the electrolyte cannot be sufficiently adsorbed 2 O). The thickness of the coating layer facing the negative electrode is 0.2-15 μm. (if the thickness is too thick, the metal oxide will be in contact withA large amount of lithium source is consumed during the lithium contact in-situ reaction, so that the service life of the battery is influenced; if the thickness is too low, the mechanical stability is poor, which affects the effective life of the protective layer).
The grain size of the functional material in the coating is 0.1-1 μm.
A method for preparing the double coated separator for simultaneously inhibiting lithium dendrite and transition metal dissolution, characterized by the steps of:
step 1: dissolving a polymer binder serving as a solute in a solvent, adding a coating functional material on the side of the diaphragm, which is opposite to the negative electrode, and uniformly mixing to obtain coating slurry; the mass ratio of the polymer binder to the solvent is 1: 50-2: 3;
the mass ratio of the polymer binder to the solvent is 1: 50-2: 3 (if the slurry is too thin, the coating surface density is unstable, the slurry is easy to settle, if the slurry is too thick, stirring is not facilitated, and inorganic matters are not uniformly dispersed).
Step 2: coating the obtained slurry on one side of a base film, and drying to evaporate the solvent, namely forming a coating on the base film;
and step 3: dissolving a polymer binder serving as a solute in a solvent, adding a coating functional material on the side of a diaphragm, which is opposite to the positive electrode, and uniformly mixing to obtain coating slurry; the mass ratio of the polymer binder to the solvent is 1: 50-2: 3;
and 4, step 4: and coating the obtained slurry on the other side of the prepared coating-containing base film, and drying to evaporate the solvent to obtain the double-coating diaphragm.
In the step 1 and the step 3, the solvent is selected from one or more of N-methyl pyrrolidone, N-dimethylformamide, ethanol, methanol, acetone or water.
In the step 2 and the step 4, the drying temperature is 20-100 ℃, and the drying time is 10-24 h.
The drying temperature of the coating is 20-100 ℃ (when the drying temperature is too high, the size deformation or microstructure change of the diaphragm basement membrane can occur, the battery performance is influenced, and when the temperature is too low, the solvent is difficult to volatilize completely, and the battery performance is influenced). The drying time is 10-24h (the drying time is too short, the solvent is difficult to volatilize completely, and the drying time is too long, so that the microstructure of the diaphragm of the basement membrane is influenced).
A lithium metal battery using the double-coated separator for simultaneously suppressing lithium dendrite and transition metal dissolution, characterized in that: the positive electrode on the side of the positive electrode coating layer of the double-coating diaphragm is lithium cobaltate positive electrode LiCoO 2 Lithium manganate anode LiMn 2 O 4 Nickel cobalt manganese ternary positive electrode LiNi x Co y Mn 1-x-y O 2 Nickel cobalt aluminium ternary positive electrode LiNi x Co y Al 1-x-y O 2 Or a lithium-rich manganese-based positive electrode (xLi) 2 MnO 3 ·(1-x)LiMO 2 ) (ii) a The lithium negative electrode on the side of the negative electrode coating of the double-coating diaphragm is a lithium sheet and a negative electrode containing metal lithium; the electrolyte is carbonate electrolyte.
The lithium metal battery needs to be kept still for 2-24 hours before circulation.
Advantageous effects
The invention provides a double-coating diaphragm capable of simultaneously inhibiting lithium dendrite and transition metal dissolution, a preparation method and a lithium metal battery applying the diaphragm. The coating on the side, opposite to the positive electrode, of the diaphragm contains a polymer binder and a moisture absorbable material. The coating on the side of the diaphragm opposite to the negative electrode contains a polymer binder and inorganic substances capable of generating chemical and alloy reactions with lithium. Compared with the prior art, the coating on the side, facing the positive electrode, of the diaphragm prepared by the method can absorb moisture in the electrolyte of the battery, reduce the generation of hydrofluoric acid and further slow down the dissolution of transition metal of the positive electrode; the coating on the side opposite to the negative electrode is contacted with the lithium negative electrode in an electrolyte environment and stands for a period of time, inorganic matters in the coating can react with lithium in situ and are finally converted into lithium-containing alloy and lithium-containing inorganic matters, and the lithium-containing inorganic matters are used as an interface layer between negative electrode diaphragms in a circulating process to reduce interface impedance, accelerate lithium ion transmission and reduce generation of dendritic crystals. Through the excellent performance of each of the two coatings, the capacity retention rate and the cycle life of the battery are improved in a double-pipe manner.
Advantageous effects
(1) The invention provides a double-coating diaphragm capable of simultaneously inhibiting lithium dendrite and transition metal dissolution, and the related diaphragm material has good air stability, simple production process and simple and convenient steps and can be produced in a large scale.
(2) The invention provides a double-coating diaphragm capable of simultaneously inhibiting lithium dendrite and transition metal dissolution, which is used for adsorbing moisture in electrolyte, inhibiting the decomposition of the electrolyte and slowing down the dissolution of the transition metal in a high-pressure positive electrode (transition metal oxide).
(2) The invention provides a double-coating diaphragm capable of simultaneously inhibiting lithium dendrite and transition metal dissolution, which is used for in-situ generation of an interface layer (lithium-containing alloy and lithium-containing inorganic substance) between the diaphragm and a lithium metal negative electrode through chemical and alloy reaction to reduce the growth of negative electrode dendrite.
(3) The battery assembled by the double-coating diaphragm and capable of simultaneously inhibiting the dissolution of lithium dendrite and transition metal provided by the invention can show stable cycle performance, and the comprehensive performance of the battery is obviously superior to that of the lithium metal battery assembled by the current commercial common diaphragm.
Drawings
FIG. 1 shows LiNi assembled with a PP-based film selected in example 1 of the present invention, a single-coated separator obtained in step two, and a double-coated separator obtained in step four, respectively 0.8 Mn 0.1 Co 0.1 O 2 The charge-discharge cycle diagram obtained for Li batteries.
Fig. 2 is a graph of the concentration of transition metal elements in the electrolyte after cycling of the cell of fig. 1 by inductively coupled plasma mass spectrometry.
FIG. 3 shows Al selected in example 2 of the present invention 2 O 3 Respectively assembling the ceramic base membrane, the single-coating membrane obtained in the step two and the double-coating membrane obtained in the step four into LiNi 0.8 Mn 0.1 Co 0.1 O 2 Li impedance spectra obtained by ac impedance method test.
Fig. 4 is an equivalent circuit used for impedance spectrum fitting in fig. 3.
FIG. 5 shows LiMn assembled from the PE-based film selected in EXAMPLE 3, the single-coated separator obtained in step two, and the double-coated separator obtained in step four, respectively 2 O 4 The charge-discharge cycle diagram obtained for Li batteries.
Detailed Description
The invention will now be further described with reference to the following examples and drawings:
examples 1
In one aspect, the present embodiment provides a method for preparing a dual coated separator that simultaneously suppresses dissolution of lithium dendrites and transition metals, including the steps of:
the method comprises the following steps: the preparation method comprises the steps of taking polymer binder PVDF with the molecular weight of 130 ten thousand as a solute and N-methylpyrrolidone as a solvent, mixing the solute and the solvent according to the mass ratio of 1:5 to completely dissolve the solute in the solvent, then adding Molecular Sieve (MS) powder with the particle size of about 200nm, wherein the mass ratio of the PVDF to the molecular sieve is 1: and 19, stirring for 8 hours, and preparing into slurry for later use.
Step two: selecting a PP diaphragm with the size of 100mm multiplied by 25mm and the thickness of 25 mu m as a base film, and uniformly coating the prepared slurry on one side of the base film. And then putting the coated base film into an oven, drying the base film at 40 ℃ for 4h in vacuum, and then drying the base film at 80 ℃ for 12h to completely evaporate the solvent to obtain the MS | PP single-coating diaphragm with the coating thickness of 1 mu m on the side opposite to the positive electrode.
Step three: the preparation method comprises the steps of taking polymer binder PVDF with the molecular weight of 130 ten thousand as a solute and N-methylpyrrolidone as a solvent, mixing the solute and the solvent according to the mass ratio of 1:5 to completely dissolve the solute in the solvent, adding AgSe particles with the particle size of about 500nm, wherein the mass ratio of the PVDF to the molecular sieve is 1: and 9, stirring for 8 hours to prepare slurry for later use.
Step four: and (4) uniformly coating the prepared slurry on the other side of the diaphragm obtained in the second step. And putting the coated diaphragm into a vacuum oven, drying for 4h at 40 ℃ in vacuum, drying for 12h at 80 ℃ to completely evaporate the solvent to obtain the MS | PP | AgSe double-coated diaphragm with the thickness of 1 μm at the side opposite to the positive electrode and the thickness of 5 μm at the side opposite to the negative electrode.
Step five: punching the base film, the MS | PP single-coating diaphragm obtained in the step two and the MS | PP | AgSe double-coating diaphragm obtained in the step four into a wafer by using a die, and mixing the wafer with LiNi 0.8 Mn 0.1 Co 0.1 O 2 The anode is matched with a lithium plate and contains 10 wt% of fluorine1M LiPF of ethylene carbonate 6 DEC (volume ratio 1:1) is used as electrolyte to assemble the button cell, a coating on one side of the positive electrode is over against the positive electrode during assembly, and a coating on one side of the negative electrode is over against the negative electrode. After standing for 12 hours, the charge and discharge test was performed.
FIG. 1 shows LiNi formed by assembling a PP-based film, an MS | PP single-coating membrane obtained in step two, and an MS | PP | AgSe double-coating membrane obtained in step four according to the present embodiment 0.8 Mn 0.1 Co 0.1 O 2 The charge-discharge cycle chart of the | Li battery is shown, wherein a PP basal membrane and an MS | PP single-coating diaphragm are used as comparative examples. As can be seen from fig. 1, the battery assembled by the MS | PP | AgSe double-coating separator shows excellent cycle stability, and the capacity retention rate after 100 cycles is as high as 98.9%, which is higher than the cycle retention rate after 100 cycles of the battery assembled by the MS | PP separator (92.4%) and the PP base film (83%) respectively containing the single coating. Fig. 2 is a graph of the transition metal element concentration in the electrolyte after cycling of the cell of fig. 1 by inductively coupled plasma mass spectrometry. After the MS | PP | AgSe double-coating diaphragm circulates, the concentration of transition metal elements contained in the electrolyte is similar to that of a single-coating diaphragm and is far lower than that of a PP basal membrane, and therefore the coating on the side, facing the positive electrode, of the diaphragm successfully inhibits the dissolution of the transition metal.
EXAMPLES example 2
In one aspect, the present embodiment provides a method for preparing a dual coated separator that simultaneously suppresses dissolution of lithium dendrites and transition metals, including the steps of:
the method comprises the following steps: the preparation method comprises the steps of taking polymer binder PVDF-HFP with the molecular weight of 200 ten thousand as solute and tetrahydrofuran as solvent, mixing the solute and the solvent according to the mass ratio of 1: 6 to completely dissolve the solute in the solvent, then adding MOF powder with the particle size of about 500nm, stirring for 8 hours, and preparing into slurry for later use.
Step two: selecting Al with the size of 100mm multiplied by 25mm and the thickness of 20 mu m 2 O 3 The ceramic diaphragm is a base film, and the prepared slurry is uniformly coated on one side of the base film. Putting the coated base film into a vacuum oven, drying at 25 ℃ for 2h in vacuum, drying at 60 ℃ for 12h to completely evaporate the solvent to obtain MOF | Al with the thickness of 5 μm on the side opposite to the anode 2 O 3 A single coated separator.
Step three: using polymer binder PVDF-HFP with molecular weight of 200 ten thousand as solute, using tetrahydrofuran as solvent, mixing solute and solvent according to mass ratio of 1: 6 to make solute completely dissolve in solvent, then adding SbF whose grain size is about 200nm 2 Powder of PVDF-HFP with SbF 2 The mass ratio of the raw materials is 1: 18, the raw materials are stirred for 8 hours, and slurry is prepared for standby.
Step four: and (4) uniformly coating the prepared slurry on the other side of the diaphragm obtained in the second step. Putting the coated diaphragm into a vacuum oven, drying for 2h at 25 ℃ in vacuum, drying for 12h at 60 ℃ to ensure that the solvent is completely evaporated to obtain MOF | Al with the thickness of 5 μm at the side opposite to the positive electrode and the thickness of 4 μm at the side opposite to the negative electrode 2 O 3 |SbF 2 A double coated separator.
Step five: al used in the above 2 O 3 Ceramic-based film and MOF | Al obtained in step two 2 O 3 Single-coating membrane and MOF | Al obtained in step four 2 O 3 |SbF 2 Punching a double-coating diaphragm into a wafer by using a die, and respectively mixing the wafer with LiNi 0.8 Mn 0.1 Co 0.1 O 2 The anode is matched with a lithium plate, and 1M LiPF is selected 6 DEC and EMC (volume ratio 1:1) are used as electrolyte to assemble the button cell, and during assembly, the coating on one side of the positive electrode is opposite to the positive electrode, and the coating on one side of the negative electrode is opposite to the negative electrode. After standing for 12h, the impedance spectrum was measured using the ac impedance method.
FIG. 3 shows Al used in the present example 2 O 3 Ceramic-based film and MOF | Al obtained in step two 2 O 3 Single-coating membrane and MOF | Al obtained in step four 2 O 3 |SbF 2 LiNi respectively assembled by double-coating membranes 0.8 Mn 0.1 Co 0.1 O 2 The impedance spectrum of the Li battery is shown in the attached table 1, wherein Al is the fitting result of the impedance spectrum 2 O 3 Ceramic-based film and MOF | Al 2 O 3 A single coated separator is a comparative example. Obviously, containing SbF 2 The interface impedance of the diaphragm and the electrode of the coating is as low as 79.4 omega, which is far lower than that of Al 2 O 3 Interfacial resistance (153. OMEGA.) and MOF | Al of ceramic-based film and electrode 2 O 3 Single coated membrane (183.6 Ω). Fig. 4 is an equivalent circuit used to fit the impedance spectrum in fig. 3. In addition, the fitting results in table 1 show SbF 2 The introduction of the composite coating enables Al 2 O 3 Base film and MOF | Al 2 O 3 The interfacial ionic transfer resistance and charge transfer resistance of the separator and the electrode were reduced from 70.2 Ω and 111.4 Ω, 50.2 Ω and 101.4 Ω to 12.1 Ω and 64.3 Ω, respectively, which indicates that the introduction of the separator coating on the side facing the negative electrode greatly improved the ionic charge transfer rate between the separator electrodes.
EXAMPLE 3
In one aspect, the present embodiment provides a method for preparing a dual coated separator that simultaneously suppresses dissolution of lithium dendrites and transition metals, including the steps of:
the method comprises the following steps: the preparation method comprises the steps of taking polymer binder PVDF with the molecular weight of 130 ten thousand as a solute, taking N-methylpyrrolidone as a solvent, mixing the solute and the solvent according to the mass ratio of 1:5 to completely dissolve the solute in the solvent, and then adding porous SiO with the particle size of about 100nm 2 Powder of PVDF and SiO 2 The mass ratio of the raw materials is 1: 18, the raw materials are stirred for 10 hours, and slurry is prepared for standby.
Step two: selecting a PE diaphragm with the size of 100mm multiplied by 25mm and the thickness of 15 mu m as a base film, and uniformly coating the prepared slurry on one side of the base film. Putting the coated base film into a vacuum oven, vacuum drying at 40 deg.C for 4h, drying at 80 deg.C for 12h to evaporate the solvent completely to obtain SiO with a coating thickness of 1 μm on the side opposite to the anode 2 L PE single coated separator.
Step three: using polymer binder PAA with molecular weight of 5 ten thousand as solute, using water as solvent, mixing solute and solvent according to mass ratio of 1: 7 to make solute completely dissolve in solvent, then adding SnCl whose grain size is about 100nm 2 And AgSe powder in a ratio of 1: and (1) stirring for 10h to prepare slurry for later use, wherein the mass ratio of the PAA to the total mass of the powder is 1: 17.
Step four: and (4) uniformly coating the prepared slurry on the other side of the diaphragm obtained in the second step. Putting the coated membrane into a vacuum oven, vacuum drying at 50 deg.C for 4 hr, and drying at 80 deg.C for 12 hr to evaporate solvent completelyTo obtain SiO with the thickness of 2 μm at the side opposite to the anode and the thickness of 2 μm at the side opposite to the cathode 2 |PE|SnCl 2 And the diaphragm is coated with the AgSe double layer.
Step five: the used PE base film and the SiO obtained in the step two 2 I PE single-coating diaphragm and SiO obtained in step four 2 |PE|SnCl 2 The [ AgSe ] double-coating diaphragm is punched into a wafer by using a die and is respectively mixed with LiMn 2 O 4 The anode is matched with a lithium plate, and 1M LiPF is selected 6 DEC and EMC (volume ratio 1:1) are used as electrolyte to assemble the button cell, and during assembly, the coating on one side of the positive electrode is opposite to the positive electrode, and the coating on one side of the negative electrode is opposite to the negative electrode. After standing for 14 hours, charge and discharge tests were performed.
FIG. 5 shows the PE-based film used in the present embodiment, SiO obtained in step two 2 The SiO obtained in the fourth step is the diaphragm with the single PE coating layer 2 |PE|SnCl 2 LiMn respectively assembled by | AgSe double-coating diaphragms 2 O 4 Charge-discharge cycle diagram of Li battery, in which PE-based film and SiO 2 The PE single coated separator is a comparative example. As can be seen from FIG. 5, SiO 2 |PE|SnCl 2 The battery assembled by the AgSe double-coating diaphragm shows excellent cycle stability, and the capacity retention rate is up to 92 percent after 100 cycles of 1C multiplying power charge-discharge cycle and is higher than that of SiO 2 The cycle retention of the batteries assembled with the PE single-coated separator (81.6%) and the PE base film (72.5%) after 100 cycles, respectively.
Table 1 shows the results of the equivalent circuit fitting of the impedance spectrum shown in FIG. 3
Wherein R is b Represents the bulk impedance, R f Represents the ion transfer resistance, R CT Represents the charge transfer resistance, R int Represents the interface impedance, consisting of ion transfer impedance and charge transfer impedance.
Claims (10)
1. A double-coated diaphragm for suppressing the release of Li dendrite and transition metal features that it contains basic film and two coated layersThe side coating is respectively opposite to the anode or the cathode; the coating comprises a polymer binder and functional materials in a mass ratio of 1: 2-20, wherein: the functional material in the coating layer at the side opposite to the positive electrode is a moisture absorbable material, and H can be stored 2 A porous inorganic material of O molecules; the functional material in the coating layer facing the negative electrode is an inorganic substance capable of chemically and alloy reacting with lithium, namely a non-lithium element in the lithium-rich alloy and a non-metal element capable of forming a stable inorganic compound with lithium.
2. The dual coated separator for simultaneous suppression of lithium dendrite and transition metal dissolution according to claim 1 wherein: the base film is a ceramic base film, a polyethylene PE base film, a polypropylene PP base film, a polypropylene/polyethylene/polypropylene multi-layer base film, a polyethylene glycol terephthalate (PET) base film, a Polyacrylonitrile (PAN) base film, a glass fiber base film, a cellulose base film or a polyvinylidene fluoride (PVDF) base film.
3. The dual coated separator for simultaneous suppression of lithium dendrite and transition metal dissolution according to claim 1 wherein: the polymer binder is: the weight-average molecular weight of the composite material is 5-300 ten thousand by one or a combination of more of sodium carboxymethylcellulose (CMC), styrene butadiene latex (SBR), polyvinylidene fluoride (PVDF), poly (vinylidene fluoride-hexafluoropropylene) PVDF-HFP, polyethylene oxide (PEO), polyacrylic acid (PAA) or polyvinylpyrrolidone (PVP).
4. The dual coated separator for simultaneous suppression of lithium dendrite and transition metal dissolution according to claim 1 wherein: the thickness of the coating on the side of the diaphragm opposite to the anode is 0.1-5 mu m, and the thickness of the coating on the side of the diaphragm opposite to the cathode is 0.2-15 mu m.
5. The dual coated separator for simultaneously suppressing lithium dendrites and transition metal dissolution according to claim 1 wherein: the grain size of the functional material in the coating is 0.1-1 μm.
6. A method for preparing the double coated separator for simultaneously suppressing lithium dendrite and transition metal dissolution according to any one of claims 1 to 5, characterized by the steps of:
step 1: dissolving a polymer binder serving as a solute in a solvent, adding a coating functional material on the side of the diaphragm, which is opposite to the negative electrode, and uniformly mixing to obtain coating slurry; the mass ratio of the polymer binder to the solvent is 1: 50-2: 3;
step 2: coating the obtained slurry on one side of a base film, and drying to evaporate a solvent, namely forming a coating on the base film;
and 3, step 3: dissolving a polymer binder serving as a solute in a solvent, adding a coating functional material on the side of a diaphragm, which is opposite to the positive electrode, and uniformly mixing to obtain coating slurry; the mass ratio of the polymer binder to the solvent is 1: 50-2: 3;
and 4, step 4: and coating the obtained slurry on the other side of the prepared coating-containing base film, and drying to evaporate the solvent to obtain the double-coating diaphragm.
7. The method of claim 6, wherein: in the step 1 and the step 3, the solvent is selected from one or more of N-methyl pyrrolidone, N-dimethylformamide, ethanol, methanol, acetone or water.
8. The method of claim 6, wherein: in the step 2 and the step 4, the drying temperature is 20-100 ℃, and the drying time is 10-24 h.
9. A lithium metal battery using the double-coated separator for simultaneously suppressing elution of lithium dendrites and transition metals according to any one of claims 1 to 5, characterized in that: the anode at the side of the anode coating layer of the double-coating diaphragm is lithium cobaltate anode LiCoO 2 Lithium manganate anode LiMn 2 O 4 Nickel cobalt manganese ternary positive electrode LiNi x Co y Mn 1-x-y O 2 Nickel cobalt aluminium ternary positive electrode LiNi x Co y Al 1-x-y O 2 Or lithium-rich manganese-based positive electrode (xLi) 2 MnO 3 ·(1-x)LiMO 2 ) (ii) a And is twoThe lithium negative electrode on the negative electrode coating side of the coating diaphragm is a lithium sheet and a negative electrode containing metal lithium; the electrolyte is carbonate electrolyte.
10. The lithium metal battery of claim 1, wherein: the lithium metal battery needs to be kept still for 2-24 hours before circulation.
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