CN112635915A - Modified diaphragm for metal lithium cathode and preparation method and application thereof - Google Patents
Modified diaphragm for metal lithium cathode and preparation method and application thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title abstract description 22
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Images
Classifications
-
- 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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/134—Electrodes based on metals, Si or alloys
-
- 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
Abstract
The invention provides a modified diaphragm for a metal lithium negative electrode and a preparation method and application thereof. The modified membrane comprises a base membrane and a modification layer coated on the base membrane; the raw material components for preparing the modification layer comprise a carbon material, a functional assistant and a lithium-containing surfactant; the mass ratio of the carbon material to the functional assistant to the lithium-containing surfactant is (5-9): (1-2): 1. when the modified diaphragm is attached to one side of a lithium metal cathode and placed when a lithium ion battery is prepared, the modified layer has the functions of storing and conducting lithium ions and can promote the uniform distribution and deposition of the lithium ions on the surface of the lithium cathode; the generation position of the negative electrode SEI is changed from the conventional direct growth on the surface of the lithium negative electrode to the in-situ growth on the surface of the carbon layer, so that the repeated generation and decomposition of the lithium negative electrode SEI along with the huge volume change of the lithium negative electrode and the consumption of active lithium are eliminated; the volume change in the charging and discharging process of the lithium negative electrode can be self-adapted, and the macroscopic volume change on the negative electrode side is controllable.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a modified diaphragm for a lithium metal cathode and a preparation method and application thereof.
Background
In recent years, with the rapid development of industries such as electronics, information, and new energy automobiles, new energy storage devices have become the focus of scientific and technical development, and research and development of high-performance and large-capacity lithium ion batteries have become the research hot spot in the field of new energy and materials at present. Lithium ion batteries have played a critical role in many fields due to their advantages of high energy density, high operating voltage, long service life, environmental friendliness, and the like. At present, although the commercial mass production of the lithium battery taking graphite (with the specific capacity of 372mAh/g) as the negative electrode is realized, with the increase of the demand for high-capacity negative electrode materials, the traditional graphite with low specific capacity can hardly meet the development requirements of energy storage devices, and the development of the high-capacity secondary battery taking lithium metal as the negative electrode becomes the leading hotspot problem of international research again. Compared with the traditional graphite, the lithium metal negative electrode has ultrahigh energy density, the theoretical specific capacity of the lithium metal negative electrode is 3860mAh/g, which is ten times of the specific capacity of the graphite, and the volume density of the lithium metal negative electrode is low (0.534 g/cm)3) And has the most negative reduction potential (-3.040V, relative to hydrogen standard potential), is a long-term negative solution replacing graphite.
However, the cycling of lithium metal has been the most significant problem limiting its application, as it can be attributed to three aspects: (1) uneven deposition of metallic lithium surface: with the increase of the cycle number, lithium dendrite is gradually formed on the surface of the metal lithium, and the metal lithium continues to grow to form dead lithium, so that lithium pulverization and cavities are caused, electrolyte and active lithium are consumed in the process, the coulombic efficiency of the battery is reduced, and the polarization of the battery is increased due to the accumulation of the dendrite and the dead lithium, which jointly cause the rapid attenuation of the capacity of the battery, and in addition, the lithium dendrite and the pulverized metal lithium can also cause a series of safety problems of possible internal short circuit of the battery, thermal failure of the battery, even explosion and the like: (2) interface instability: the active lithium metal electrode is in contact with electrolyte and part of solid electrolyte to generate chemical reactions/electrochemical reactions with different degrees, and the SEI formed at the same time can be repeatedly generated and decomposed along with the generation of dendritic lithium metal and the volume change of the lithium metal electrode, so that the electrolyte and active lithium are continuously consumed, and meanwhile, the accumulation of side reaction products with poor lithium ion conductivity can cause polarization increase. (3) Volume change of metallic lithium: the absolute volume change of the metal lithium in the charging and discharging processes reaches up to 100%, and the SEI is cracked due to the huge volume change, so that the SEI is repeatedly generated and decomposed; in particular, for a lithium metal battery using a solid electrolyte, since the solid electrolyte is a relatively rigid and non-flowable substance, volume expansion/contraction of lithium of a negative electrode during charge and discharge, coupled with pulverization consumption of the lithium metal due to non-directional dissolution and deposition on the surface of the lithium metal, a partial void layer occurs between the electrolyte and the negative electrode of the lithium metal, and such void layer causes breakage of a lithium ion transport path and gradual increase of internal resistance of the battery, thereby causing a decline in battery capacity.
In order to solve the cycling problem of metallic lithium, considering process amplification and application feasibility, constructing a metallic lithium stabilizing interface layer (artificial SEI), and guiding uniform lithium deposition are the most direct and efficient solutions. At present, it is common practice to introduce various additives, such as Vinylene Carbonate (VC), FEC and other solvents, and LTFSL, LiFSI, LiNOj and other lithium salts, into the existing electrolyte, and by introducing an SEI component with higher stability and stronger structure, consumption of active lithium by SEI decomposition can be reduced to a certain extent, but long-term cycle performance still needs to be improved urgently.
Based on the above SEI repair, researchers have recently proposed the construction of artificial interfacial layers, also called artificial SEIs, on lithium metal surfaces, such asSiO2、Al2O3Physically modified interfaces such as polyacetylene, and LizN, LiPO4The chemical modified interface with the ion conduction function such as PEO plays a more obvious role in guiding lithium to be uniformly deposited and improving the short-term lithium cycle performance, however, because the chemical modified interface lacks the binding force with the metal lithium and lacks the elasticity, when the volume of the metal lithium is changed in the charging and discharging process, the interface layer is easy to fall off, so that the chemical modified interface is difficult to play a role in blocking the direct contact between the metal lithium and the electrolyte and inhibiting lithium dendrite in long cycle. In addition, the prior art generally adopts a method for directly modifying the metallic lithium, but because the metallic lithium is extremely active, the treatment must be carried out in a drying room with extremely low dew point; because the treatment usually involves the use of a solvent, the chemical stability of the metal lithium and the solvent, the process problems of surface wrinkles, even breakage, difficulty in winding and unwinding and the like of the metal lithium caused by solvent volatilization, and the potential safety hazard caused by a large amount of heat generation caused by possible side reactions need to be considered at the same time. Although the method can relieve the circulation problem of the metal lithium, the related effects are usually in the stages of material development, manual process, button cell and other small-sized cell verification, and an automatic process amplification method for improving and verifying the circulation performance of a ampere-hour-grade large cell is not available.
Disclosure of Invention
Based on the defects of the prior art, the first object of the invention is to provide a modified diaphragm for a metallic lithium negative electrode; the modified diaphragm can maintain good structural stability, can be self-adaptive to volume change in the charging and discharging processes of metal lithium, has the functions of homogenizing lithium ion flow and guiding lithium to be uniformly deposited, can be applied to the metal lithium battery, can obviously improve the cycle stability of a lithium cathode, and has a simple and safe preparation process; the second purpose of the invention is to provide a preparation method of the modified diaphragm; the third purpose of the invention is to provide the application of the modified diaphragm in the lithium ion battery metal lithium negative electrode; the fourth purpose of the invention is to provide a lithium ion battery containing the modified diaphragm.
The purpose of the invention is realized by the following technical means:
in one aspect, the invention provides a modified diaphragm for a lithium metal cathode, which comprises a base film and a modification layer coated on the base film;
the raw material components for preparing the modification layer comprise a carbon material, a functional assistant and a lithium-containing surfactant;
the mass ratio of the carbon material to the functional assistant to the lithium-containing surfactant is (5-9): (1-2): 1.
when the modified diaphragm is attached to one side of a lithium metal cathode of a battery and placed when a lithium ion battery is prepared, the modified diaphragm has the functions of storing and conducting lithium ions based on a Fermi balance mechanism, and promotes the uniform distribution and deposition of the lithium ions on the surface of the lithium cathode; the generation position of the negative electrode SEI is changed from the conventional direct growth on the surface of the lithium negative electrode to the in-situ growth on the surface of the carbon layer, so that the repeated generation and decomposition of the lithium negative electrode SEI along with the huge volume change of the lithium negative electrode and the consumption of active lithium caused by the repeated generation and decomposition of the lithium negative electrode SEI are eliminated; the volume change in the charging and discharging process of the lithium negative electrode can be self-adapted, and the macroscopic volume change on the negative electrode side is controllable.
The carbon material in the modification layer can chemically react with the metal lithium cathode, so that a lithium ion storage medium based on a Fermi balance mechanism is provided, a buffer space is provided for a lithium ion flow reaching the cathode side, and the problem of uneven deposition of lithium ions such as dendrites and holes caused by uneven local concentration of the lithium ion flow is avoided; the functional auxiliary agent in the modification layer can provide necessary lithium ion transmission sites, can carry out lithium ion transmission and conduction, and has a material bonding function; the lithium-containing surfactant in the modification layer can avoid the introduction of other cations as impurities and the interference of other cations on lithium ion conduction, and provide a necessary lithium ion conduction source; on the other hand, the solvent absorption property of the modified separator can be improved, and the solvent content can be reduced.
In the modified diaphragm, preferably, the thickness of the base film is 10-25 μm, and the thickness of the modification layer is 1-20 μm; preferably 5 to 15 μm.
In the modified membrane, the base membrane is preferably selected from any one of a polyethylene membrane, a polypropylene membrane, a polyethylene/polypropylene double-layer membrane, a polypropylene/polyethylene/polypropylene triple-layer membrane, and a polyimide membrane, but is not limited thereto. The content of each raw material in the double-layer diaphragm and the three-layer diaphragm can be any, and can be selected according to the routine operation in the field.
In the modified membrane, the carbon material preferably includes one or more of activated carbon, graphene oxide, carbon nanotubes, ketjen black, Super-P, acetylene black, and graphite, but is not limited thereto.
In the modified diaphragm, the functional assistant preferably includes one or more of polypropylene alcohol, polyacrylamide, polyvinyl amide, polyacrylic acid, polyacrylonitrile, polymethyl methacrylate, polyethylene carbonate, urethane acrylate, polyvinyl carbonate, polyethylene carbonate, polypropylene carbonate, and polybutylene carbonate, but is not limited thereto.
In the modified separator, preferably, the lithium-containing surfactant includes one or more of lithium fatty alcohol polyoxyethylene ether sulfate, lithium alkyl phosphate, lithium alkyl sulfate, lithium alkylbenzene sulfonate, lithium polyacrylate, lithium alkylbenzene sulfonate, and lithium alkyl glyceryl ether sulfonate, but is not limited thereto.
On the other hand, the invention also provides a preparation method of the modified diaphragm, which comprises the following steps:
mixing and dispersing a carbon material, a functional assistant and a lithium-containing surfactant in an organic solvent in a sand grinding manner according to a proportion to obtain slurry;
and uniformly coating the slurry on one surface of the base film, drying to obtain the modified diaphragm, and attaching the modified diaphragm to one side of the negative electrode when assembling the battery.
During the drying process, the organic solvent is essentially volatilized, and a small amount of residue does not affect the electrical properties.
In the above preparation method, preferably, the organic solvent includes one or more of N-methylpyrrolidone, dimethylformamide, dimethylsulfoxide and acetone, but is not limited thereto.
In the above-mentioned preparation method, the organic solvent is used for dispersing the three solid components and coating, and the amount thereof is not limited.
In the preparation method, preferably, the sum of the functional assistant and the surfactant accounts for 1 wt% to 20 wt% of the slurry, and the solid content of the slurry is 5 wt% to 70 wt%.
In the preparation method, preferably, the drying temperature is 80-150 ℃ after the slurry is uniformly coated on the surface of the base film; preferably 100 to 130 ℃.
In another aspect, the invention also provides an application of the modified diaphragm in a lithium ion battery metal lithium negative electrode.
In the above application, preferably, the modified layer of the modified separator is placed on one side of the lithium metal negative electrode.
In another aspect, the invention further provides a lithium ion battery, which comprises the modified diaphragm.
The invention has the beneficial effects that:
(1) when the modified layer of the modified diaphragm is attached to one side of the metal lithium cathode of the battery and placed, the modified layer is always attached to the metal lithium, and a carbon layer (such as a multi-walled carbon nanotube (MCNT)) is not a pure physical barrier layer but becomes an interface layer through chemical reaction with the metal lithium, and the reaction mechanism is as follows: when a carbon material is brought into intimate contact with lithium, an electrochemical potential (also called contact potential) is generated driven by the fermi balance; the spontaneous reaction of reduction and lithiation of the carbon material is initiated to generate a Li-C composite interface containing SEI on the surface, so that a physical interface is evolved into a chemical composite interface to grow on the surface of the metal lithium, deposition and desorption of the metal lithium are generated below the interface layer, the interface layer can generate a follow-up effect according to the volume change of the metal lithium, and the shedding and failure in the process are avoided, thereby ensuring that the regulation and control effect on uniform deposition of the lithium is maintained in long circulation.
(2) The stability of the modified diaphragm interface layer per se is as follows: SEI is formed on the surface of a carbon layer (such as MCNT), and the framework of the SEI is kept unchanged, so that the integrity of the SEI is maintained, the barrier function of isolating Li from an electrolyte is fully exerted, and active lithium consumption caused by repeated generation and decomposition of the SEI generated by direct contact of lithium and the electrolyte is avoided.
(3) The modified diaphragm of the invention guides lithium to be uniformly deposited: on one hand, the modified diaphragm is used as a dynamic 'solvent storage tank' which enables lithium ions to freely enter and exit, when the battery is charged, the lithium ions stored by the modified diaphragm are distributed on the surface of the metal lithium in a dense and uniform ion flow mode, so that uniform deposition on the surface of the metal lithium is promoted, and the similar effect that the growth time of lithium dendrites is prolonged by similar high-concentration lithium salt so as to reduce the lithium dendrites is achieved; the dynamic replenishment of lithium ions comes from the metallic lithium negative electrode as the battery is discharged. On the other hand, the modified diaphragm is used as a transfer station of lithium ions, so that lithium deposition does not occur in the interior or on the surface of the diaphragm, and the problems of dendrite generation, diaphragm puncture and the like are caused.
(4) The functional auxiliary agent in the modification layer of the modified diaphragm can provide necessary lithium ion transmission sites, can transfer and conduct lithium ions, and has a material bonding function; the lithium-containing surfactant in the modification layer can avoid the introduction of other cations as impurities and the interference of other cations on lithium ion conduction, and provide a necessary lithium ion conduction source; on the other hand, the solvent absorption property of the modified separator can be improved, and the solvent content can be reduced.
(5) The modified diaphragm preparation process can realize process compatibility, easy amplification and controllable thickness by coating on the diaphragm or other substrates, and avoids a series of safety problems of harsh environmental requirements (which are required to be carried out in an environment with extremely low dew point), difficult process amplification, side reaction of lithium and a solvent, violent heat release and the like caused by treatment on metal lithium.
Drawings
FIG. 1 shows that the modified separator of example 1 of the present invention and the unmodified separator of comparative example 1 are lmA/cm2(Current), 1mAh/cm2Comparative plot of polarization curves for symmetric cells under (deposition amount) conditions.
FIG. 2 shows the results of the comparison of the modified separator of example 1 of the present invention and the unmodified separator of comparative example 1 at 2mA/cm2(Current, 1 mAh/cm)2Pair under (deposition amount) conditionThe cell polarization curve is referred to as a contrast graph.
Detailed Description
The technical solutions of the present invention will be described in detail below in order to clearly understand the technical features, objects, and advantages of the present invention, but the present invention is not limited to the practical scope of the present invention.
Example 1:
the embodiment provides a modified diaphragm for a metal lithium negative electrode and a preparation method thereof, and the modified diaphragm comprises the following steps:
(1) mixing the multi-wall carbon nano-tube: polyacrylic acid: lithium polyacrylate (mass ratio) is uniformly dispersed in N-methylpyrrolidone (NMP) by sanding (diameter of the sanded zirconium beads: 1.8 mm-2.0 mm, rotating speed: 2500r/min), and solid content is controlled to be 5 wt%, so that slurry of the modification layer is obtained.
(2) And (3) selecting a polypropylene (PP) diaphragm with the thickness of 14 mu m as a base film, and coating the slurry in the step (1) on the surface of the base film by using a coating machine in a micro-gravure coating mode, wherein the coating thickness is 10 mu m. Drying in a drying oven at 80 ℃ for 5min, transferring into a vacuum oven, vacuum drying at 50 ℃ for 20h, cooling, and taking out to obtain a modified diaphragm; the modification layer is uniformly attached to the surface of the basement membrane, and is uniform in thickness and 2 microns.
The embodiment also provides a lithium ion battery and a preparation method thereof, and the preparation method comprises the following steps:
the modified diaphragm prepared above was used as an intermediate diaphragm, metal lithium foils were respectively placed on both sides, a CR2032 button cell of Li/modified diaphragm/Li system was assembled with EC and DEC (volume ratio 1:1) solution of 1M LIPF6 as electrolyte, and a lithium-lithium symmetric cell polarization curve test was performed, and the experimental results are shown in fig. 1 and fig. 2.
Comparative example 1:
the comparative example provides an unmodified diaphragm assembled lithium ion battery, which specifically comprises the following steps:
a CR2032 button cell of Li/separator/Li system was assembled with a polypropylene (PP) separator of 14 μ M as a middle separator, metal lithium foils on both sides, and EC and DEC (1: 1 by volume) solutions of 1M LIPF6 as electrolytes, and polarization curve test of unmodified Li/basement membrane/Li symmetric cell was performed, and the experimental results are shown in fig. 1.
Fig. 1 and 2 are polarization curves of an unmodified Li/base film/Li (comparative example 1) and a Li/modified separator/Li (example 1) symmetric battery. Wherein, FIG. 1 is lmA/cm2(Current), 1mAh/cm2Symmetric cell polarization curves under (deposition amount) conditions; FIG. 2 shows 2mA/cm2(Current, 1 mAh/cm)2Symmetric cell polarization curves under (deposition amount) conditions.
As can be seen from fig. 1 and 2: the polarization potential of example 1 was 10mV and remained stable for up to 100h or more, whereas the polarization potential of comparative example 1 was up to 100mV and showed a tendency of increasing polarization after 100 h. The description shows that the modified layer in example 1 fully exerts its function as a dynamic "solvent storage cell" in which lithium ions can freely enter and exit, and when the battery is charged, the lithium ions stored in the modified layer are deposited on the surface of the metal lithium in a dense and uniform ion flow, so that the overpotential of lithium deposition is reduced, and the uniform deposition on the surface of the metal lithium is promoted, and therefore, the polarization potential of only 10mV is presented. Meanwhile, the SEI is formed on the surface of the carbon layer in the embodiment 1, the stability of the carbon layer frame well maintains the integrity of the SEI, and the barrier function of isolating Li from the electrolyte is fully exerted, so that the polarization potential can be kept stable in long-term circulation. In the comparative example 1, since the SEI is positioned on the surface of lithium, the volume change of the lithium causes the repeated decomposition and generation of the SEI, a poor conductor of lithium ions generated by the reaction is mixed with dead lithium and is attached to the surface of the metal lithium, so that the polarization potential of lithium deposition is continuously increased, and the lithium deposited in a non-uniform way forms dendrites when the cycle reaches a certain time and is accumulated, so that the battery is finally short-circuited, and the potential returns to zero after violent oscillation.
Table 1 compares the performance of the modified separator of example 1 with the unmodified separator of comparative example 1.
Table 1:
as can be seen from a comparison of table 1: the modified separator (example 1) had superior thermal stability (lower thermal shrinkage) and enhanced mechanical strength (needle punching strength, etc.) compared to the unmodified separator (comparative example 1).
Example 2:
the embodiment provides a modified diaphragm for a metal lithium negative electrode and a preparation method thereof, and the modified diaphragm comprises the following steps:
(1) mixing the multi-wall carbon nano-tube: polyacrylic acid: lithium polyacrylate (6: 1:1 (mass ratio)) is uniformly dispersed in dimethylformamide by sanding (the diameter of the sanding zirconium beads: 1.8-2.0 mm, and the rotating speed: 3000r/min), and the solid content is controlled to be 5 wt%, so that the slurry of the modification layer is obtained.
(2) And (3) selecting a polypropylene (PP) diaphragm with the thickness of 12 microns as a base film, and coating the slurry in the step (1) on the surface of the base film by using a coating machine in a micro-gravure coating mode, wherein the coating thickness is 10 microns. Drying in a drying oven at 80 ℃ for 5min, transferring into a vacuum oven, vacuum drying at 60 ℃ for 12h, cooling, and taking out to obtain a modified diaphragm; the modification layer is uniformly attached to the surface of the basement membrane, and is uniform in thickness and 2 microns.
The embodiment also provides a lithium ion battery and a preparation method thereof, and the preparation method comprises the following steps:
with high nickel ternary positive electrode material (Li (Ni)0.8Mn0.1Co0.1)O2NCM811) is a positive electrode material, and is prepared by mixing NCM811, a carbon black conductive agent (SP), polyvinylidene fluoride (PVDF) in a mass ratio of 97% to 1.3% to 1.7%, coating, rolling, punching and baking the pole piece, wherein the loading capacity is 44mg/cm2And the size is 12mm in diameter.
Using the prepared NCM811 with the diameter of 12mm as a positive electrode plate, the prepared modified diaphragm as an intermediate diaphragm in the embodiment, dropwise adding 1mol/L of ethylene carbonate and dimethyl carbonate solution of lithium hexafluorophosphate as electrolyte, and finally covering a conventional metal lithium sheet with the diameter of 14mm as a negative electrode plate, sealing, and completing the assembly of the button cell; wherein, the modification layer of the modified diaphragm is attached to one side of the metal lithium sheet for placement.
Comparative example 2:
the comparative example provides an unmodified diaphragm assembled lithium ion battery, which specifically comprises the following steps:
with high nickel ternary positive electrode material (Li (Ni)0.8Mn0.1Co0.1)O2NCM811) is a positive electrode material, and is prepared by mixing NCM811, a carbon black conductive agent (SP), polyvinylidene fluoride (PVDF) in a mass ratio of 97% to 1.3% to 1.7%, coating, rolling, punching and baking the pole piece, wherein the loading capacity is 44mg/cm2And the size is 12mm in diameter.
And (3) taking the NCM811 with the diameter of 12mm obtained by the preparation as a positive pole piece, taking a polypropylene (PP) diaphragm as an intermediate diaphragm, dropwise adding an lmol/L ethylene carbonate and dimethyl carbonate solution of lithium hexafluorophosphate as an electrolyte, finally covering a conventional metal lithium piece with the diameter of 14mm as a negative pole piece, sealing, and finishing the assembly of the button cell.
Comparative example 3:
the comparative example prepared a modified membrane without added lithium-containing surfactant, the comparative modified membrane prepared by the process of:
(1) mixing the multi-wall carbon nano-tube: polyacrylic acid was uniformly dispersed in dimethylformamide at a ratio of 6:1 (mass ratio) by sanding (diameter of zirconium beads by sanding: 1.8mm to 2.0mm, rotation speed: 3000r/min) with a solid content of 5 wt% to obtain a slurry for a finish layer.
(2) And (3) selecting a polypropylene (PP) diaphragm with the thickness of 12 microns as a base film, and coating the slurry in the step (1) on the surface of the base film by using a coating machine in a micro-gravure coating mode, wherein the coating thickness is 10 microns. Drying in a drying oven at 80 ℃ for 5min, transferring into a vacuum oven, vacuum drying at 60 ℃ for 12h, cooling, and taking out to obtain a modified diaphragm; the modification layer is uniformly attached to the surface of the basement membrane, and is uniform in thickness and 2 microns.
The present comparative example also provides a lithium ion battery and a method of making the same, comprising the steps of:
with high nickel ternary positive electrode material (Li (Ni)0.8Mn0.1Co0.1)O2NCM811) is a positive electrode material, and is prepared by mixing NCM811, carbon black conductive agent (SP), polyvinylidene fluoride (PVDF) in a mass ratio of 97% to 1.3% to 1.7%, coating, and rollingPressing and punching the pole piece, baking to prepare an NCM811 positive pole piece with the carrying capacity of 44mg/cm2And the size is 12mm in diameter.
Using the prepared NCM811 with the diameter of 12mm as a positive pole piece, using the prepared modified diaphragm as an intermediate diaphragm, dropwise adding 1mol/L ethylene carbonate and dimethyl carbonate solution of lithium hexafluorophosphate as electrolyte, finally covering a conventional metal lithium piece with the diameter of 14mm as a negative pole piece, sealing, and finishing the assembly of the button cell; wherein, the modification layer of the modified diaphragm is attached to one side of the metal lithium sheet for placement.
The batteries prepared in example 2, comparative example 2 and comparative example 3 were subjected to charge and discharge performance tests, and the results of the tests are shown in table 2.
Table 2:
| first coulombic efficiency | Discharge capacity/mAh/g | Cycle number @ capacity retention ratio | |
| Example 2 | 90.7％ | 192.4 | [email protected]％ |
| Comparative example 2 | 89.9％ | 190.3 | [email protected]％ |
| Comparative example 3 | 89.5％ | 189.5 | 12@79％ |
As can be seen from a comparison of table 2:
example 2 maintained 80% capacity retention after 167 cycles, while comparative example 2 had dropped its capacity to below 80% after 100 cycles, confirming that the modification layer grown on the lithium surface has significant advantages in leading uniform deposition of lithium ions, maintaining SEI structure stability, reducing active lithium consumption and pulverization, etc.
The capacity maintenance rate of example 2 was still as high as 80% after 167 cycles, while the capacity maintenance rate of comparative example 3 dropped below 80% after 12 cycles, indicating that the selection of functional adjuvants and lithium-containing surfactants is critical for the performance of the battery. In particular, the absence of added lithium-containing surfactants results in loss of active lithium, while the by-products lead to increased polarization, which results in rapid decay of the battery cycle.
Example 3:
the embodiment provides a modified diaphragm for a metal lithium negative electrode and a preparation method thereof, and the modified diaphragm comprises the following steps:
(1) mixing the multi-wall carbon nano-tube: polyethylene oxide: lithium polyacrylate (6: 2: 1) is uniformly dispersed in Dimethylformamide (DMF) by sanding (diameter of zirconium beads is 1.8 mm-2.0 mm, rotating speed is 3000r/min), and solid content is controlled to be 8 wt%, so that the slurry of the modification layer is obtained.
(2) And (3) selecting a polypropylene (PP) diaphragm with the thickness of 12 microns as a base film, and coating the slurry in the step (1) on the surface of the base film by using a coating machine in a micro-gravure coating mode, wherein the coating thickness is 15 microns. Drying in a drying oven at 80 ℃ for 5min, transferring into a vacuum oven, vacuum drying at 70 ℃ for 12h, cooling, and taking out to obtain a modified diaphragm; the modifying layer is uniformly attached to the surface of the basement membrane, and the thickness of the modifying layer is uniform and 2.7 mu m.
The embodiment also provides a lithium ion battery and a preparation method thereof, and the preparation method comprises the following steps:
with high nickel ternary positive electrode material (Li (Ni)0.8Mn0.1Co0.1)O2NCM811) is a positive electrode material, and is prepared by mixing NCM811, a carbon black conductive agent (SP), polyvinylidene fluoride (PVDF) in a mass ratio of 97% to 1.3% to 1.7%, coating, rolling, punching and baking the pole piece, wherein the loading capacity is 44mg/cm2And the size is 70mm by 60 mm.
Using the prepared NCM811 as a positive electrode plate, the prepared modified diaphragm as an intermediate diaphragm, dropwise adding 1mol/L of lithium hexafluorophosphate in ethylene carbonate and dimethyl carbonate solution as electrolyte, finally covering metal lithium (with the thickness of 50 μm and the size of 72mm × 62mm) as a negative electrode plate, stacking and assembling the 1Ah soft package battery, heating for primary packaging, and performing secondary packaging by vacuum air suction; wherein, the modification layer of the modified diaphragm is attached to one side of the metal lithium sheet for placement.
Comparative example 4:
the comparative example provides an unmodified diaphragm assembled lithium ion battery, which specifically comprises the following steps:
with high nickel ternary positive electrode material (Li (Ni)0.8Mn0.1Co0.1)O2NCM811) is a positive electrode material, and is prepared by mixing NCM811, a carbon black conductive agent (SP), polyvinylidene fluoride (PVDF) in a mass ratio of 97% to 1.3% to 1.7%, coating, rolling, punching and baking the pole piece, wherein the loading capacity is 44mg/cm2And the size is 12mm in diameter.
The NCM811 positive pole piece prepared in the above way, 1mol/L ethylene carbonate and dimethyl carbonate solution of lithium hexafluorophosphate are used as electrolyte, a metal lithium (thickness of 50um, size of 72mm x 62mm) negative pole Piece and Polypropylene (PP) are used as diaphragms, the 1Ah soft package battery is assembled by stacking, heating is carried out for primary packaging, and then vacuum air suction is carried out for secondary packaging.
The batteries prepared in example 3 and comparative example 4 were subjected to charge and discharge performance tests, and the results of the tests are shown in table 3.
Table 3:
| first coulombic efficiency | Discharge capacity/mAh/g | Cycle number @ capacity retention ratio | |
| Example 3 | 85.7％ | 209.4 | 33@83％ |
| Comparative example 4 | 83.8％ | 207.6 | 6@79％ |
As can be seen from a comparison of table 3: the laminate battery using the modified diaphragm shows higher coulombic efficiency and better cyclicity, and shows that the carbon modified layer provided by the invention has positive effects on reducing the contact between electrolyte and lithium metal and guiding the uniform deposition of lithium.
Claims (10)
1. A modified diaphragm for a metal lithium cathode comprises a base film and a modification layer coated on the base film;
the raw material components for preparing the modification layer comprise a carbon material, a functional assistant and a lithium-containing surfactant;
the mass ratio of the carbon material to the functional assistant to the lithium-containing surfactant is (5-9): (1-2): 1.
2. the modified membrane according to claim 1, wherein the base film has a thickness of 10 to 25 μm; the thickness of the modification layer is 1-20 μm, preferably 5-15 μm.
3. The modified membrane according to claim 1, wherein the base membrane is selected from any one of a polyethylene membrane, a polypropylene membrane, a polyethylene/polypropylene double-layer membrane, a polypropylene/polyethylene/polypropylene triple-layer membrane, and a polyimide membrane.
4. The modified separator of claim 1, wherein the carbon material comprises one or more of activated carbon, graphene oxide, carbon nanotubes, ketjen black, Super-P, acetylene black, and graphite.
5. The modified separator of claim 1, wherein the functional additive comprises one or more of polypropylene glycol, polyacrylamide, polyvinyl amide, polyacrylic acid, polyacrylonitrile, polymethyl methacrylate, polyethylene carbonate, urethane acrylate, polyethylene carbonate, polypropylene carbonate, and polybutylene carbonate.
6. The modified separator of claim 1, wherein the lithium-containing surfactant comprises one or more of lithium fatty alcohol polyoxyethylene ether sulfate, lithium alkyl phosphate, lithium alkyl sulfate, lithium alkyl benzene sulfonate, lithium polyacrylate, lithium alkyl benzene sulfonate, and lithium alkyl glyceryl ether sulfonate.
7. A method for preparing the modified separator as claimed in any one of claims 1 to 6, which comprises the steps of:
mixing and dispersing a carbon material, a functional assistant and a lithium-containing surfactant in an organic solvent in a sand grinding manner according to a proportion to obtain slurry;
and uniformly coating the slurry on one surface of the base film, and drying to obtain the modified diaphragm.
8. The production method according to claim 7, wherein the organic solvent includes one or more of N-methylpyrrolidone, dimethylformamide, dimethyl sulfoxide, and acetone;
preferably, the drying temperature after the slurry is uniformly coated on the surface of the base film is 80-150 ℃; preferably 100 to 130 ℃.
9. The application of the modified separator of any one of claims 1 to 6 in a lithium ion battery lithium metal negative electrode;
preferably, the modified diaphragm is placed by being attached to one side of the lithium metal negative electrode.
10. A lithium ion battery comprising the modified separator as defined in any one of claims 1 to 6.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113193300A (en) * | 2021-04-30 | 2021-07-30 | 湖南立方新能源科技有限责任公司 | Diaphragm, preparation method thereof and lithium metal battery |
| CN113745636A (en) * | 2021-09-08 | 2021-12-03 | 湖南立方新能源科技有限责任公司 | Solid-state lithium battery and preparation method thereof |
| CN113991245A (en) * | 2021-10-27 | 2022-01-28 | 中国工程物理研究院电子工程研究所 | Modified particle-loaded fiber diaphragm for thermal battery and preparation method thereof |
| CN114094275A (en) * | 2021-11-05 | 2022-02-25 | 珠海冠宇电池股份有限公司 | Diaphragm and battery containing same |
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| CN115207483A (en) * | 2022-07-27 | 2022-10-18 | 欣旺达电子股份有限公司 | Solid-state battery and electric equipment |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102008046498A1 (en) * | 2008-09-10 | 2010-03-11 | Li-Tec Battery Gmbh | Electrode and separator material for lithium-ion cells and process for their preparation |
| JP2014067632A (en) * | 2012-09-26 | 2014-04-17 | Kyoritsu Kagaku Sangyo Kk | Ceramic slurry for protecting battery electrode or separator |
| JP2016103439A (en) * | 2014-11-28 | 2016-06-02 | 協立化学産業株式会社 | Slurry composition, method for manufacturing the same, and coated body formed by use thereof |
| CN106784543A (en) * | 2017-03-14 | 2017-05-31 | 中国人民解放军63971部队 | It is a kind of to prevent barrier film protective coating of metal negative electrode dendrite short circuit and preparation method thereof |
| CN108832060A (en) * | 2018-05-31 | 2018-11-16 | 中国科学院物理研究所 | Composite diaphragm and its preparation method and application for lithium battery |
| CN109950459A (en) * | 2019-03-26 | 2019-06-28 | 广东九州太阳能科技有限公司 | A kind of lithium ion battery separator of richness lithium |
| CN110911619A (en) * | 2019-12-19 | 2020-03-24 | 昆山宝创新能源科技有限公司 | Lithium battery diaphragm, preparation method thereof and lithium battery |
-
2020
- 2020-12-21 CN CN202011517120.0A patent/CN112635915A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102008046498A1 (en) * | 2008-09-10 | 2010-03-11 | Li-Tec Battery Gmbh | Electrode and separator material for lithium-ion cells and process for their preparation |
| JP2014067632A (en) * | 2012-09-26 | 2014-04-17 | Kyoritsu Kagaku Sangyo Kk | Ceramic slurry for protecting battery electrode or separator |
| JP2016103439A (en) * | 2014-11-28 | 2016-06-02 | 協立化学産業株式会社 | Slurry composition, method for manufacturing the same, and coated body formed by use thereof |
| CN106784543A (en) * | 2017-03-14 | 2017-05-31 | 中国人民解放军63971部队 | It is a kind of to prevent barrier film protective coating of metal negative electrode dendrite short circuit and preparation method thereof |
| CN108832060A (en) * | 2018-05-31 | 2018-11-16 | 中国科学院物理研究所 | Composite diaphragm and its preparation method and application for lithium battery |
| CN109950459A (en) * | 2019-03-26 | 2019-06-28 | 广东九州太阳能科技有限公司 | A kind of lithium ion battery separator of richness lithium |
| CN110911619A (en) * | 2019-12-19 | 2020-03-24 | 昆山宝创新能源科技有限公司 | Lithium battery diaphragm, preparation method thereof and lithium battery |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113193300A (en) * | 2021-04-30 | 2021-07-30 | 湖南立方新能源科技有限责任公司 | Diaphragm, preparation method thereof and lithium metal battery |
| CN113745636A (en) * | 2021-09-08 | 2021-12-03 | 湖南立方新能源科技有限责任公司 | Solid-state lithium battery and preparation method thereof |
| CN113991245A (en) * | 2021-10-27 | 2022-01-28 | 中国工程物理研究院电子工程研究所 | Modified particle-loaded fiber diaphragm for thermal battery and preparation method thereof |
| CN114094275A (en) * | 2021-11-05 | 2022-02-25 | 珠海冠宇电池股份有限公司 | Diaphragm and battery containing same |
| CN114243211A (en) * | 2021-11-09 | 2022-03-25 | 中国计量大学 | Lithium battery diaphragm capable of inhibiting gas production and lithium battery |
| CN115207483A (en) * | 2022-07-27 | 2022-10-18 | 欣旺达电子股份有限公司 | Solid-state battery and electric equipment |
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