CN112751140B - Diaphragm functional coating material for improving liquid retention capacity and safety performance of lithium ion battery electrolyte - Google Patents
Diaphragm functional coating material for improving liquid retention capacity and safety performance of lithium ion battery electrolyte Download PDFInfo
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- CN112751140B CN112751140B CN201910985173.6A CN201910985173A CN112751140B CN 112751140 B CN112751140 B CN 112751140B CN 201910985173 A CN201910985173 A CN 201910985173A CN 112751140 B CN112751140 B CN 112751140B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- 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 application relates to the technical field of lithium ion batteries, in particular to a diaphragm functional coating material for improving the liquid retention amount and safety performance of lithium ion battery electrolyte. The oxide ceramic in the coating material of the application adopts g-C with porous and larger specific surface area 3 N 4 The polymer material is used as a carrier to realize the uniform distribution of the polymer material in the coating, and g-C 3 N 4 The introduction of the polymer increases the mechanical property and flexibility of the coating, so that the specific gravity of the oxide ceramic in the coating can be obviously increased, the heat resistance of the diaphragm containing the coating can be improved, the diaphragm is prevented from being heated and contracted, and the safety performance of overcharge, short circuit, furnace temperature and the like of the battery containing the diaphragm is further improved.
Description
Technical Field
The application relates to the technical field of lithium ion batteries, in particular to a coating material based on graphite-phase carbon nitride/oxide ceramics, which can improve the liquid retention amount of electrolyte of a lithium ion battery and the safety performance of overcharge, short circuit and the like of the lithium ion battery.
Background
The lithium ion battery has the advantages of higher energy density, longer cycle life, environmental friendliness and the like, and is widely applied to portable electronic products such as mobile phones, notebook computers and the like and new energy automobiles. However, for lithium ion batteries, cycle life and safety are two of the most important contents, especially for power lithium ion batteries, the life of the current new energy automobile is shortened and safety accidents frequently occur. Therefore, the improvement of the cycle life and the safety performance of the lithium ion battery becomes a serious thing in the lithium ion battery.
In lithium ion batteries, the addition amount (liquid retention amount) of electrolyte is a key factor influencing the cycle life of the battery, and particularly for soft-package batteries with low space utilization rate, the improvement of the liquid retention amount is quite limited on the premise of ensuring no liquid expansion. Therefore, the lithium ion battery can generate polarization increase caused by electrolyte consumption in long-term circulation, and the circulation performance is drastically reduced, thereby greatly shortening the service life of the battery. The use of the diaphragm ceramic coating enhances the hardness of the diaphragm, reduces the heat shrinkage of the diaphragm, relieves the possibility of puncturing the diaphragm by lithium dendrites, and can greatly improve the safety performance of the battery.
Current ceramic separator coatings are typically prepared from ceramic particles, which typically use alumina, and in addition, silica, magnesia, calcia, etc. may also be used as ceramic particles. Ceramic powder on the market can be divided into two qualities of high purity (99.99%, particle size 0.3-1.0 μm) and refining (99.7%, particle size 0.3-2.5 μm), wherein the former can be uniformly distributed in slurry without further grinding; the latter has relatively poor dispersibility, requires further grinding processing to be uniformly dispersed in the slurry, has high process requirements for coating manufacturers, requires stable control, and increases cost.
For a slurry of a certain concentration, the higher the ceramic particle mass ratio, the higher the hardness of the coated membrane, the better the thermal performance, but the mechanical and cyclic properties are reduced, because too many ceramic particles reduce the coating uniformity and weaken the backbone structure of the polymeric binder. And the ceramic material has low porosity, low specific surface area and low liquid retention, and is easy to block diaphragm pores, so that a lithium ion transmission channel of the battery is blocked, the internal resistance of the battery is increased, and the cycle performance of the battery is reduced.
Disclosure of Invention
In order to overcome the defects in the prior art, the application aims to provide a diaphragm functional coating material for improving the liquid retention capacity and safety performance of lithium ion battery electrolyte, a preparation method thereof and application thereof in a diaphragm. The application prepares graphite-phase carbon nitride (g-C) by a hydrothermal method-solid phase reaction method two-step method 3 N 4 ) g-C based on an even distribution of oxide ceramics as support 3 N 4 Coating material of oxide ceramic.
Higher energy density is the target of continuous challenges for lithium ion batteries, but safety performance and cycle life are also facing increasing challenges, and finding a way to improve the amount of liquid retention and safety performance on the separator coating is the most straightforward method. The applicant finds out that the coating material which is easy to disperse, easy to combine with oxide ceramics, good in mechanical property, large in porosity and specific surface area, low in price and easy to prepare through a large amount of research, can promote the dispersion of the oxide ceramics in slurry, ensures that the oxide ceramics are uniformly distributed in a diaphragm coating, increases the mass ratio of the oxide ceramics, and has no poor mechanical property, and more importantly, the porosity and the specific surface area are large, so that the electrolyte retention amount of the battery can be increased, and the method has great significance in improving the cycle performance and the safety performance of the lithium ion battery.
Graphite phase carbon nitride (g-C) 3 N 4 ) Is a typical polymer semiconductor with a planar second surface approximating grapheneA lamellar structure. g-C 3 N 4 Has good thermal stability and chemical stability. g-C 3 N 4 The heat stability of the material can be reduced when the temperature exceeds 600 ℃, and the structural performance is kept stable under strong acid and strong alkali, so that the material is nontoxic, environment-friendly and free of secondary pollution. g-C 3 N 4 The preparation method is simple and has lower cost. g-C 3 N 4 The conventional preparation methods of (a) are classified into a solid phase reaction method, a solvothermal method, an electrochemical deposition method and a thermal polymerization method. The composite material prepared by compounding graphite-phase carbon nitride and oxide ceramic is used for coating the diaphragm for the first time, so that various defects of the conventional ceramic-based diaphragm are overcome. Further, the application also provides a modified graphite phase carbon nitride which is different from the conventional method and has a specific surface area larger than the g-C prepared by the conventional method 3 N 4 Specific surface area (in the range of 40-50m 2 About/g), and the porosity is far greater than that of g-C prepared by the conventional method 3 N 4 (the porosity is generally lower), the uniform combination with oxide ceramics is better realized, and the method is more beneficial to improving the liquid retention amount of the electrolyte of the lithium ion battery and the safety performance such as overcharge, short circuit and the like of the lithium ion battery.
The specific technical scheme of the application is as follows:
the coating material comprises graphite-phase carbon nitride and oxide ceramic, wherein the graphite-phase carbon nitride is used as a carrier, and the oxide ceramic is uniformly distributed on the surface of the graphite-phase carbon nitride carrier.
According to the application, the oxide ceramic is also uniformly distributed in the pores of the graphite phase carbon nitride.
According to the application, the particle size of the oxide ceramic is nanoscale.
According to the present application, the graphite phase carbon nitride is a modified graphite phase carbon nitride.
According to the present application, the graphite phase carbon nitride is carbonyl-modified graphite phase carbon nitride.
According to the application, the mass ratio of the graphite phase carbon nitride to the oxide ceramic is 1:19-19:1.
A method of preparing a coating material, the method comprising the steps of:
(1) Dissolving a carbon-nitrogen monomer in an organic solvent to prepare a carbon nitride precursor mixed system;
(2) Dissolving a ceramic precursor in water to prepare a ceramic precursor mixed system;
(3) Mixing the carbon nitride precursor mixed system in the step (1) and the ceramic precursor mixed system in the step (2), optionally adjusting the pH to be alkaline, and then performing hydrothermal reaction to prepare a precursor of the ceramic coating material;
(4) And (3) roasting the precursor of the ceramic coating material in the step (3) to prepare the coating material.
According to the present application, in the step (1), the organic solvent is an organic solvent containing a carboxyl group, for example, one or more selected from formic acid, acetic acid, propionic acid, butyric acid, oxalic acid, benzoic acid.
According to the application, in step (2), the ceramic precursor is selected from TiO 2 Ceramic precursors (e.g. tetrabutyl titanate (TBT), titanyl sulfate (TiOSO) 4 ) One or two of them), siO 2 Ceramic precursors (e.g. alkyl orthosilicates, such as ethyl orthosilicate (TEOS), al) 2 O 3 Ceramic precursors (e.g. sodium metaaluminate (NaAlO) 2 ) Potassium metaaluminate (KAlO) 2 ) One or more of these soluble meta-aluminates), mgO ceramic precursors (e.g., magnesium chloride (MgCl) 2 ·H 2 O), magnesium nitrate (Mg (NO) 3 ) 2 ) One or more of these soluble magnesium salts).
According to the application, in the step (3), the carbon nitride precursor mixed system in the step (1) is added dropwise into the ceramic precursor mixed system in the step (2).
A coating material prepared by the above preparation method.
A separator coating comprising the coating material described above.
According to the application, in the membrane coating, the coating material comprises 1-99wt%, preferably 20-60wt%, of the total mass of the membrane coating.
According to the application, the thickness of the membrane coating is 0.1 μm to 10. Mu.m, preferably 1 μm to 5. Mu.m.
A separator comprising a base layer and a separator coating as described above.
The preparation method of the diaphragm comprises the following steps:
and mixing the coating material, the binder and optionally the solvent to prepare mixed slurry, coating the mixed slurry on at least one side surface of the base layer, drying, and compacting to prepare the diaphragm.
According to the application, the solid content in the mixed slurry is 30-90wt%, i.e. the mass percentage of the coating material is 30-90wt%.
A battery comprising the separator described above.
The application has the beneficial effects that:
(1) The coating material of the application comprises graphite phase carbon nitride (i.e. g-C 3 N 4 Polymer material) and oxide ceramic, wherein the oxide ceramic is in the form of a porous, g-C with a large specific surface area 3 N 4 The polymer material is used as a carrier to realize the uniform distribution of the polymer material in the coating, and g-C 3 N 4 The introduction of the polymer increases the mechanical property and flexibility of the coating, so that the specific gravity of oxide ceramics in the coating can be obviously increased, the heat resistance of a diaphragm applying the coating can be improved, the diaphragm is prevented from being heated and contracted, and the safety performance of overcharge, short circuit, furnace temperature and the like of a battery containing the diaphragm is further improved.
(2) The coating material disclosed by the application has the advantages of higher porosity and larger specific surface area. Therefore, the diaphragm comprising the coating material can greatly improve the electrolyte retention amount of the lithium ion battery, thereby improving the cycle performance and the service life of the battery.
(3) The coating material disclosed by the application is easy to prepare, low in cost, stable in structural performance under strong acid and strong alkali, resistant to hydrofluoric acid corrosion caused by electrolyte side reaction, nontoxic, environment-friendly, free of secondary pollution and easy to prepare and produce on a large scale.
Drawings
FIG. 1 is a graph showing the 3C/1C100% DOD cycle performance at room temperature of the batteries prepared in examples 1-5 and comparative examples 1-3.
Detailed Description
As described above, the present application provides a coating material, which includes graphite-phase carbon nitride and oxide ceramic, wherein the graphite-phase carbon nitride is used as a carrier, and the oxide ceramic is uniformly distributed on the surface of the graphite-phase carbon nitride carrier.
Wherein, because the graphite phase carbon nitride has a porous structure, the oxide ceramic is also uniformly distributed in the pores of the graphite phase carbon nitride, such as the pores inside the graphene carbon nitride carrier.
Wherein the particle size of the oxide ceramic may be nano-sized.
Wherein the oxide ceramic is at least one selected from aluminum oxide, magnesium oxide, silicon oxide, titanium oxide and the like.
Wherein the mass ratio of the graphite phase carbon nitride to the oxide ceramic is 1:19-19:1, for example, 1:9-9:1, such as 1:4-4:1, such as 1:1.
Wherein the graphite phase carbon nitride is a modified graphite phase carbon nitride, specifically, a carbonyl modified graphite phase carbon nitride. Specifically, the molecular formula in the two-dimensional lamellar structure of pure graphite phase carbon nitride is shown as formula I, the two-dimensional lamellar structure has a complete plane structure, and the two-dimensional lamellar structure is tightly combined together, has fewer defects, but has lower specific surface area (40-50 m 2 Per g), low porosity<15％)。
The molecular formula in the two-dimensional lamellar structure of the carbonyl modified graphite-phase carbon nitride is shown as formula II, a carbonyl group is introduced into the structure shown as formula I (namely, the carbonyl group is introduced into the structure shown as formula I in the hydrothermal process by adopting the hydrothermal method of the application), and the carbon nitride is conductiveSo that defects appear in the planar structure, the specific surface area is increased, and CO is generated after high-temperature roasting 2 Gas, such that the porosity increases. Thus, the porosity and specific surface area of the graphite-phase carbon nitride carrier can be remarkably improved.
Wherein, during the hydrothermal reaction, the oxide ceramic can be bonded with graphite-phase carbon nitride through chemical bonding. Specifically, taking carbonyl modified graphite phase carbon nitride as an example, the electron-rich carbonyl C=O group is easily combined with the electron-free oxide metal element or nonmetal element to form a coordination bond (shown in the following formula III, wherein X is a metal element), so that the ceramic precursor is uniformly dispersed in g-C 3 N 4 After high-temperature roasting, the nano oxide ceramic is formed into g-C with larger specific surface area and larger porosity 3 N 4 Is formed at the aperture of the plate.
Wherein the specific surface area of the coating material>500m 2 Permeability of the mixture/g>40％。
Illustratively g-C 3 N 4 /Al 2 O 3 、g-C 3 N 4 /MgO、g-C 3 N 4 /SiO 2 And g-C 3 N 4 /TiO 2 The specific surface areas of the coating materials are respectively 550-630m 2 /g、550-620m 2 /g、520-600m 2 /g and 520-600m 2 And/g, the porosity is between 40% and 48%.
As described above, the present application also provides a method for preparing a coating material, the method comprising the steps of:
(1) Dissolving a carbon-nitrogen monomer in an organic solvent to prepare a carbon nitride precursor mixed system;
(2) Dissolving a ceramic precursor in water to prepare a ceramic precursor mixed system;
(3) Mixing the carbon nitride precursor mixed system in the step (1) and the ceramic precursor mixed system in the step (2), optionally adjusting the pH to be alkaline, and then performing hydrothermal reaction to prepare a precursor of the ceramic coating material;
(4) And (3) roasting the precursor of the ceramic coating material in the step (3) to prepare the coating material.
In step (1), the carbon nitrogen monomer is selected from melamine or urea.
In the step (1), the organic solvent is an organic solvent containing a carboxyl group, for example, selected from formic acid, acetic acid, propionic acid, butyric acid, oxalic acid, benzoic acid, and the like. The introduction of the carboxyl groups may increase the specific surface area of the carbon nitride material, see in particular the discussion hereinabove regarding carbonyl-modified graphite phase carbon nitrides.
In the step (1), the mass fraction of the carbon-nitrogen monomer in the carbon nitride precursor mixed system is 1-50wt%, for example, 1wt%, 2wt%, 5wt%, 10wt%, 12wt%, 15wt%, 18wt%, 20wt%, 25wt%, 30wt%, 35wt%, 40wt%, 45wt%, 50wt%.
In the step (1), when the organic solvent is selected from carboxylic acids, the organic solvent may be added in the form of an aqueous carboxylic acid solution having a concentration of 1% or more and less than 100%.
In step (2), the ceramic precursor is selected from TiO 2 Ceramic precursors (e.g. tetrabutyl titanate (TBT), titanyl sulfate (TiOSO) 4 ) Etc., siO 2 Ceramic precursors (e.g. alkyl orthosilicates, such as ethyl orthosilicate (TEOS), al 2 O 3 Ceramic precursors (e.g. sodium metaaluminate (NaAlO) 2 ) Potassium metaaluminate (KAlO) 2 ) Isosoluble meta-aluminates), mgO ceramic precursors (e.g. magnesium chloride (MgCl) 2 ·H 2 O), magnesium nitrate (Mg (NO) 3 ) 2 ) And/or soluble magnesium salts).
In the step (2), the mass fraction of the ceramic precursor in the ceramic precursor mixed system is 1-80wt%, for example
In step (3), the mixing is, for example, adding the carbon nitride precursor mixed system of step (1) dropwise to the ceramic precursor mixed system of step (2).
In the step (3), the volume ratio of the carbon nitride precursor mixed system in the step (1) to the ceramic precursor mixed system in the step (2) is 1:19-19:1.
In step (3), the pH of the mixed system is adjusted to be alkaline, e.g. pH >8, using sodium hydroxide. Preferably, when the ceramic precursor is selected from MgO ceramic precursors, the pH of the mixed system is adjusted to be alkaline with sodium hydroxide.
In the step (3), the hydrothermal reaction is performed in a sealed reaction kettle, and the volume space of the mixed system accounts for 20-90%.
In the step (3), the temperature of the hydrothermal reaction is 160-260 ℃, and the time of the hydrothermal reaction is 3-48 hours.
In the step (3), the method further comprises the following post-treatment steps: filtering and drying the product after hydrothermal reaction to prepare the precursor of the ceramic coating material with uniform distribution.
In step (4), the calcination is performed under an inert atmosphere, which may be, for example, nitrogen.
In step (4), the calcination is performed in a muffle furnace or a tube furnace.
In the step (4), the roasting temperature is 450-580 ℃, and the roasting time is 3-12 hours.
The application also provides the coating material prepared by the method.
The application also provides a diaphragm coating, which comprises the coating material.
Wherein the separator coating further comprises a binder.
Wherein the binder is selected from an oily binder or an aqueous binder, and the oily binder is selected from at least one of PVDF5130, HSV900 and Kynar 761A; the aqueous binder is at least one selected from PTFE emulsion, SBR emulsion and PAA emulsion aqueous binder.
In the membrane coating, the coating material accounts for 1-99wt%, preferably 20-60wt%, of the total mass of the membrane coating.
Wherein the thickness of the separator coating is 0.1 μm to 5 μm, preferably 1 μm to 2 μm.
The application also provides a diaphragm, which comprises a base layer and the diaphragm coating.
The base layer is a common base layer of a diaphragm for a lithium ion battery, and can be a PP diaphragm base layer, a PE diaphragm base layer or a diaphragm base layer formed by mixing a PP layer and a PE layer.
The application also provides a preparation method of the diaphragm, which comprises the following steps:
and mixing the coating material, the binder and optionally the solvent to prepare mixed slurry, coating the mixed slurry on at least one side surface of the base layer, drying, and compacting to prepare the diaphragm.
Wherein the solid content in the mixed slurry is 30-90wt%, i.e. the mass percentage of the coating material is 30-90wt%.
Wherein the solvent is at least one selected from N-methyl pyrrolidone (NMP), N-dimethyl amide (DMF) and dimethyl sulfoxide (DMSO).
Wherein, if the binder is selected from oily binders, the mixed slurry comprises a solvent.
The application also provides a battery, which comprises the separator.
The battery is a lithium ion battery, such as a coiled lithium ion battery or a laminated lithium ion battery.
The preparation method of the present application will be described in further detail with reference to specific examples. It is to be understood that the following examples are illustrative only and are not to be construed as limiting the scope of the application. All techniques implemented based on the above description of the application are intended to be included within the scope of the application.
The experimental methods used in the following examples are all conventional methods unless otherwise specified; the reagents, materials, etc. used in the examples described below are commercially available unless otherwise specified.
Example 1
(1)g-C 3 N 4 /Al 2 O 3 Preparation of ceramic coated diaphragm S1
And dissolving melamine in an acetic acid solution through stirring to obtain a mixed system A with the mass fraction of melamine being 30%. Sodium metaaluminate (NaAlO) was added by stirring 2 ) Dissolving in an aqueous solution to obtain a mixed system B with the mass fraction of sodium metaaluminate of 30%.
And (3) dropwise adding the mixed system A into the mixed system B, and stirring the mixed system B while dropwise obtaining a mixed system C, wherein the volume ratio of the mixed system A to the mixed system B is 1:1. The mixed system C is placed in a sealed reaction kettle, the volume space ratio of the mixed system C in the reaction kettle is 70%, the heating temperature is 180 ℃, and the heating time is 8 hours. And after hydrothermal reaction, filtering, drying and collecting a sample.
The g-C obtained above 3 N 4 /Al 2 O 3 The precursor is introduced into N 2 Is placed in a tubular furnace at 520 ℃ for high-temperature sintering for 5 hours under the gas environment to prepare the g-C with uniform distribution 3 N 4 /Al 2 O 3 Porous, large specific surface area ceramic coating materials.
g-C in the ceramic coating material 3 N 4 And Al 2 O 3 The mass ratio of (2) is 1:1.
The g-C obtained above 3 N 4 /Al 2 O 3 The ceramic coating material and the binder PVDF are stirred at high speed to obtain a uniformly dispersed mixture. In the mixture, g-C 3 N 4 /Al 2 O 3 The ceramic coating material accounts for 20 weight percent. The mixture was prepared into a membrane ceramic coating slurry having a solid content of 70wt% using N-methylpyrrolidone (NMP) as a solvent. Uniformly coating the slurry on two sides of a PP diaphragm, drying and compacting to obtain the porous and large specific surface area g-C 3 N 4 /Al 2 O 3 The thickness of the single-sided coating of the diaphragm of the ceramic coating material is 1 μm.
(2) Preparation of positive electrode sheet P1
And mixing the ternary nickel cobalt manganese NCM of the positive electrode active material, the binder PVDF and the conductive carbon black, and stirring at a high speed to obtain a uniformly dispersed mixture. In the mixture, the solid component contained 95wt% of NCM, 2wt% of binder PVDF, and 3wt% of conductive carbon black. The mixture was prepared into a positive electrode active material slurry using N-methylpyrrolidone as a solvent, and the solid content in the slurry was 70wt%. The slurry is uniformly coated on two sides of an aluminum foil, and is dried and compacted by a roller press to obtain a positive plate which is marked as P1.
(3) Preparation of negative plate N1
The artificial graphite is used as an active substance, SBR binder, thickener sodium carboxymethylcellulose and conductive carbon black Super-P as conductive agent, and the mixture containing the negative electrode active substance is prepared by high-speed stirring to obtain a uniformly dispersed mixture. The solid component of the mixture contained 95wt% of artificial graphite, 1.5wt% of sodium carboxymethyl cellulose, 1.5wt% of conductive carbon black Super-P, and 2wt% of SBR-based binder. Deionized water was used as a solvent to prepare a negative electrode active material slurry, the solid content in the slurry being 50wt%. The slurry is uniformly coated on two sides of a copper foil, and is dried and compacted by a roller press, so that a negative plate N1 is obtained.
(4) Assembly of cell C1
After the positive pole piece P1 and the negative pole piece N1 are punched, g-C is used 3 N 4 /Al 2 O 3 The ceramic coating diaphragm S1 adopts Z-shaped lamination to form a bare cell, and an aluminum tab and a copper nickel-plated tab are respectively rotated out. Clamping the bare cell by using a glass clamp with the strength of 100MPa/m 2 And baking at 85 ℃ in vacuum for 24 hours, and packaging with an aluminum plastic film. The electrolyte adopts lithium hexafluorophosphate electrolyte containing 1M, and the solvent is a mixed solvent of ethylene carbonate/dimethyl carbonate/1, 2-propylene glycol carbonate-1:1:1 (volume ratio). After packaging, the battery is formed and aged to obtain a square flexible package battery with the length and width of 160mm multiplied by 60mm multiplied by 10mm, which is marked as C1.
Example 2
Other operations are the same as in example 1, except that:
in step (1), magnesium chloride (MgCl) is stirred 2 ·H 2 O) is dissolved in the water solution to obtain the quality of magnesium chlorideThe mixed system B with the weight fraction of 30 percent is prepared to obtain g-C 3 N 4 MgO membrane ceramic coating. g-C in the ceramic coating material 3 N 4 And MgO in a mass ratio of 1:1.
I.e. g-C 3 N 4 /Al 2 O 3 g-C for diaphragm ceramic coating 3 N 4 And replacing the MgO diaphragm ceramic coating to prepare the battery C2.
Example 3
Other operations are the same as in example 1, except that:
in the step (1), titanyl sulfate (TiOSO) is added by stirring 4 ) Dissolving in water solution to obtain a mixed system B with the mass fraction of the titanyl sulfate of 30 percent, and preparing g-C 3 N 4 /TiO 2 And (3) a diaphragm ceramic coating. g-C in the ceramic coating material 3 N 4 And TiO 2 The mass ratio of (2) is 1:1.
I.e. g-C 3 N 4 /Al 2 O 3 g-C for diaphragm ceramic coating 3 N 4 /TiO 2 And replacing the diaphragm ceramic coating, wherein the prepared battery is C3.
Example 4
Other operations are the same as in example 1, except that:
in the step (1), tetraethyl orthosilicate (TEOS) is dissolved in an aqueous solution by stirring to obtain a mixed system B with the mass fraction of the tetraethyl orthosilicate of 30 percent, and g-C is prepared 3 N 4 /SiO 2 And (3) a diaphragm ceramic coating. g-C in the ceramic coating material 3 N 4 And SiO 2 The mass ratio of (2) is 1:1.
I.e. g-C 3 N 4 /Al 2 O 3 g-C for diaphragm ceramic coating 3 N 4 /SiO 2 And replacing the diaphragm ceramic coating, wherein the prepared battery is C4.
Example 5
The difference from example 1 is that:
will g-C 3 N 4 /Al 2 O 3 The thickness of the single-sided diaphragm ceramic coating is changed from 1 μm to 2 μm,the prepared battery was C5.
Example 6
The difference from example 1 is that:
the volume ratio of the mixed system A to the mixed system B is changed from 1:1 to 1:2, so that g-C in the ceramic coating material is changed from 1:1 to 1:2 3 N 4 And Al 2 O 3 The mass ratio of (2) is 1:2, and the prepared battery is C6.
Comparative example 1
The difference from example 1 is that:
g-C with 1 μm thick single side 3 N 4 /Al 2 O 3 The ceramic coating diaphragm is changed into the traditional commercialized Al with single-sided thickness of 1 mu m 2 O 3 The ceramic coated separator produced a C7 cell.
Comparative example 2
Other operations are the same as in example 1, except that:
and dissolving melamine in an acetic acid solution through stirring to obtain a mixed system A with the mass fraction of melamine being 30%. The mixed system A is placed in a sealed reaction kettle, the volume space ratio of the mixed system A in the reaction kettle is 70%, the heating temperature is 180 ℃, and the heating time is 8 hours. And after hydrothermal reaction, filtering, drying and collecting a sample. The prepared battery was C8.
Comparative example 3
Other operations are the same as in example 1, except that:
sodium metaaluminate (NaAlO) was added by stirring 2 ) Dissolving in an aqueous solution to obtain a mixed system B with the mass fraction of sodium metaaluminate of 30%.
The mixed system B is placed in a sealed reaction kettle, the volume space ratio of the mixed system B in the reaction kettle is 70%, the heating temperature is 180 ℃, and the heating time is 8 hours. And after hydrothermal reaction, filtering, drying and collecting a sample. The prepared battery was C9.
Test example 1
The prepared separator of the battery C1-C9 is tested for porosity, tensile strength, thermal shrinkage and HF acid corrosiveness, and the testing process is as follows: eight separator blocks of the C1-C9 battery are selected respectively, the shape of the separator blocks is square with the side length of 15mm, the porosity is measured by an analytical balance weighing method, the Transverse (TD) tensile strength and the longitudinal (MD) tensile strength are measured by a tensile tester, the TD and MD heat shrinkage rate are measured by an oven and steel ruler measuring method, and the corrosiveness of the coating is verified by an HF acid soaking method, and the test results are shown in Table 1.
Table 1 shows the characterization results of the battery separators prepared in examples 1-6 and comparative examples 1-3
Test example 2
And (3) testing the electrolyte retention amount of the prepared batteries C1-C9, wherein the testing process is as follows: and respectively selecting 5 batteries of C1-C9, respectively injecting electrolyte with the same mass into each battery, then aging and soaking, forming and sealing for two times, weighing and calculating the mass of the electrolyte sealed in the aluminum plastic film, namely the liquid retention amount, and testing the results shown in Table 2.
Table 2 shows the electrolyte retention results of the batteries prepared in examples 1 to 6 and comparative examples 1 to 3
| Numbering device | C1/g | C2/g | C3/g | C4/g | C5/g | C6/g | C7/g | C8/g | C9/g |
| 1# | 22.3 | 22.8 | 22.7 | 22.2 | 24.8 | 21.8 | 19.5 | 21.5 | 20.4 |
| 2# | 22.1 | 23.0 | 22.9 | 22.3 | 25.0 | 21.5 | 19.7 | 21.3 | 20.6 |
| 3# | 22.6 | 22.9 | 23.4 | 22.2 | 24.3 | 21.7 | 19.5 | 21.8 | 20.0 |
| 4# | 22.5 | 22.9 | 22.9 | 22.4 | 24.6 | 21.4 | 19.6 | 21.9 | 20.2 |
| 5# | 22.5 | 23.1 | 22.8 | 22.2 | 24.2 | 21.7 | 19.7 | 21.4 | 20.5 |
Test example 3
The safety performance test is carried out on the prepared batteries C1-C9, wherein the test process is as follows, 5 batteries of C1-C9 are respectively selected, the batteries are placed in an oven, the temperature is raised to 150 ℃ at the heating rate of 5 ℃/min, the batteries are kept for 3 hours, the batteries do not smoke or fire and are used as the standard of passing the furnace temperature test, the Pass is marked as Pass, and otherwise, the Pass is marked as NG; the test results are shown in Table 3.
Table 3 shows the safety test results of the batteries prepared in examples 1 to 6 and comparative examples 1 to 3 at a furnace temperature of 150℃for 3 hours
From Table 1, g-C can be seen 3 N 4 Oxide ceramic coated membranes are superior to conventional ceramic membranes and to pure g-C 3 N 4 The porosity and tensile strength of the coating diaphragm and the oxide ceramic coating diaphragm are greatly improved, the thermal shrinkage rate at 105 ℃ for 1h is also much smaller, the material is also resistant to corrosion of HF acid, and the material performances can obviously improve the liquid retention capacity, the cycle performance and the safety performance of the battery.
As can be seen from Table 2, the use of g-C 3 N 4 The electrolyte retention of oxide ceramic coated separator cells is greater than that of conventional ceramic separator cells, especially g-C cells 3 N 4 C5 cell with increased oxide ceramic coating thickness, with maximum liquid retention, which demonstrates porous, large specific surface area g-C 3 N 4 The introduction of the electrolyte can obviously improve the electrolyte retention amount of the lithium ion battery.
As can be seen from Table 3, g-C was used 3 N 4 Oxide ceramic coating diaphragm has much improved heat resistance than battery using traditional ceramic diaphragm, polymer g-C 3 N 4 The introduction of the ceramic oxide can improve the uniformity and the adding proportion of the ceramic oxide in the coating of the diaphragm, and enhance the hardness and the mechanical property of the diaphragm, thereby better preventing the diaphragm from shrinking and improving the safety performance of the lithium ion battery. But increase g-C 3 N 4 The proportion of ceramic oxide in the oxide ceramic coating, such as a C6 battery, can relatively reduce the porosity of the diaphragm and the liquid retention capacity of the battery, but the hardness and mechanical property of the diaphragm are improved, the heat shrinkage and the heat resistance are improved, and the safety performance of the diaphragm is improved, which indicates that the existence of graphite-phase carbon nitride polymer in the diaphragm coating can increase the specific gravity of the oxide ceramic without affecting the mechanical property of the diaphragm, so that the hardness and the heat resistance of the diaphragm are improved.
Test example 4
The 3C/1C100% DOD cycle performance test at room temperature is carried out on the prepared batteries C1-C9, the test process is as follows, firstly, the 3C constant current is charged to 4.2V, then the constant voltage is charged, the cut-off current is 0.05C, finally the 1C constant current is discharged to 2.5V, the cycle test is carried out until the capacity is attenuated to 80%, and the test result is shown in figure 1.
As can be seen from FIG. 1, g-C is used 3 N 4 Oxide ceramic coated separator film is more delayed than battery cycle water jump using conventional ceramic separator film, especially g-C 3 N 4 The cycle times of the C5 battery with the oxide ceramic coating with increased thickness can reach 1000 circles, which is improved by more than 800 circles compared with the cycle times of the traditional ceramic diaphragm battery, thus showing that the quantity of the electrolyte liquid retention plays a critical role in the cycle performance and the service life of the lithium ion battery, and the battery has the advantages of porosity and large specific surface area g-C 3 N 4 The introduction of the oxide ceramic coating can furthest improve the liquid retention amount of the electrolyte, thereby improving the cycle performance and the service life of the lithium ion battery.
In order to accelerate the circulation speed of the battery cell, the battery cell circulation test method is that the battery cell is charged to 4.2V at the room temperature of 3C, then discharged to 3.0V at the room temperature of 1C, and discharge capacity values of different circulation turns are recorded.
The embodiments of the present application have been described above. However, the present application is not limited to the above embodiment. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application should be included in the protection scope of the present application.
Claims (18)
1. The diaphragm coating material for the lithium ion battery is characterized by comprising graphite-phase carbon nitride and oxide ceramics, wherein the graphite-phase carbon nitride is used as a carrier, and the oxide ceramics are uniformly distributed on the surface and in pores of the graphite-phase carbon nitride carrier; the graphite-phase carbon nitride is carbonyl-modified graphite-phase carbon nitride;
specific surface area of the separator coating material>500m 2 /g, pore spaceRate of>40％；
The molecular formula of the two-dimensional lamellar structure of the carbonyl modified graphite phase carbon nitride is shown as a formula II:
formula II.
2. The separator coating material of claim 1, wherein the particle size of the oxide ceramic is nano-sized.
3. The separator coating material of claim 1, wherein the mass ratio of graphite phase carbon nitride to oxide ceramic is 1:19-19:1.
4. A separator coating material as claimed in any one of claims 1 to 3, wherein the separator coating material is g-C 3 N 4 /Al 2 O 3 Separator coating material, g-C 3 N 4 MgO separator coating material, g-C 3 N 4 /SiO 2 Separator coating material or g-C 3 N 4 /TiO 2 The specific surface areas of the diaphragm coating materials are respectively 550-630m 2 /g、550-620m 2 /g、520-600m 2 /g and 520-600m 2 And/g, the porosity is between 40% and 48%.
5. A method of preparing a separator coating material as claimed in any one of claims 1 to 4, comprising the steps of:
(1) Dissolving a carbon-nitrogen monomer in an organic solvent to prepare a carbon nitride precursor mixed system;
(2) Dissolving a ceramic precursor in water to prepare a ceramic precursor mixed system;
(3) Mixing the carbon nitride precursor mixed system in the step (1) and the ceramic precursor mixed system in the step (2), optionally adjusting the pH to be alkaline, and then performing hydrothermal reaction to prepare a precursor of the ceramic coating material;
(4) And (3) roasting the precursor of the ceramic coating material in the step (3) to prepare the membrane coating material.
6. The method according to claim 5, wherein in the step (2), the ceramic precursor is selected from TiO 2 Ceramic precursor, siO 2 Ceramic precursor, al 2 O 3 At least one of a ceramic precursor and an MgO ceramic precursor.
7. The production method according to claim 6, wherein in the step (2), the TiO 2 The ceramic precursor is selected from tetrabutyl titanate (TBT), titanyl sulfate (TiOSO) 4 ) One or two of the following components; the SiO is 2 The ceramic precursor is selected from alkyl orthosilicates; the Al is 2 O 3 The ceramic precursor is selected from sodium metaaluminate (NaAlO) 2 ) Potassium metaaluminate (KAlO) 2 ) One or more of the following; the MgO ceramic precursor is selected from magnesium chloride (MgCl) 2 ·H 2 O), magnesium nitrate (Mg (NO) 3 ) 2 ) One or more of the following.
8. The preparation method according to claim 5, wherein in the step (3), the carbon nitride precursor mixed system of the step (1) is added dropwise to the ceramic precursor mixed system of the step (2).
9. A separator coating comprising the separator coating material of any one of claims 1 to 4, or prepared by the preparation method of any one of claims 5 to 8.
10. The membrane coating of claim 9, wherein the membrane coating material comprises 1-99wt% of the total mass of the membrane coating.
11. The membrane coating of claim 9, wherein the membrane coating material comprises 20-60wt% of the total mass of the membrane coating.
12. The membrane coating of claim 9, wherein the membrane coating has a thickness of 0.1-10 μιη.
13. The separator coating of claim 12, wherein the separator coating has a thickness of 1-5 μιη.
14. A separator comprising a base layer and the separator coating of any of claims 9-13.
15. A method of making the separator of claim 14, comprising the steps of:
mixing the membrane coating material prepared by the preparation method of any one of claims 1-4 or 5-8 with a binder and optionally a solvent to prepare a mixed slurry, coating the mixed slurry on at least one side surface of a base layer, drying, and compacting to prepare the membrane.
16. The method for producing a separator according to claim 15, wherein the solid content in the mixed slurry is 30-90wt%, i.e., the mass percentage of the separator coating material is 30-90wt%.
17. A battery, wherein the battery comprises the separator of claim 14.
18. The battery of claim 17, the battery being a lithium ion battery.
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