CN111211278A - Composite coating diaphragm for lithium ion battery and lithium ion battery - Google Patents

Composite coating diaphragm for lithium ion battery and lithium ion battery Download PDF

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Publication number
CN111211278A
CN111211278A CN201811400131.3A CN201811400131A CN111211278A CN 111211278 A CN111211278 A CN 111211278A CN 201811400131 A CN201811400131 A CN 201811400131A CN 111211278 A CN111211278 A CN 111211278A
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China
Prior art keywords
coating
lithium ion
diaphragm
ion battery
boehmite
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CN201811400131.3A
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Chinese (zh)
Inventor
贾海
王海文
张海峰
白莉
戴静闻
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Avic Innovation Technology Research Institute Jiangsu Co ltd
China Lithium Battery Technology Co Ltd
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China Aviation Lithium Battery Co Ltd
China Aviation Lithium Battery Research Institute Co Ltd
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Priority to CN201811400131.3A priority Critical patent/CN111211278A/en
Publication of CN111211278A publication Critical patent/CN111211278A/en
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • H01M10/0525Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409Separators, membranes or diaphragms characterised by the material
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

Abstract

The invention relates to a composite coating diaphragm for a lithium ion battery and the lithium ion battery, and belongs to the technical field of lithium ion batteries. The composite coating diaphragm for the lithium ion battery comprises a diaphragm substrate and a composite coating arranged on one side of the diaphragm substrate, wherein the composite coating comprises a silica coating arranged on the diaphragm substrate and a first boehmite coating arranged on the silica coating. The silicon dioxide coating of the composite coating diaphragm for the lithium ion battery can avoid the performance attenuation and safety problems caused by the fact that the diaphragm is punctured after lithium dendrites continue to grow rapidly, the first boehmite coating coated on the surface of the silicon dioxide coating avoids the reaction of silicon dioxide and metal lithium on the surface of a negative electrode before the lithium dendrites appear, the excessive loss of effective lithium of the battery is prevented, the further growth of the lithium dendrites can be delayed, and therefore the service life of the battery is effectively prolonged, and the occurrence of safety accidents of the battery is reduced.

Description

Composite coating diaphragm for lithium ion battery and lithium ion battery
Technical Field
The invention relates to a composite coating diaphragm for a lithium ion battery and the lithium ion battery, and belongs to the technical field of lithium ion batteries.
Background
Lithium ion batteries, especially power batteries, have a relatively high energy density. The key to the production and application of the battery is to ensure the safety of the battery. In the using process of the lithium ion battery, the formation of lithium dendrite is difficult to thoroughly avoid, uncertain factors influencing the formation of the lithium dendrite are more, and the lithium ion battery is a potential hidden danger in the using process of the battery.
Lithium dendrite growth is one of the fundamental problems affecting the safety and stability of lithium ion batteries. The growth of the lithium dendrites can cause the instability of an electrode and an electrolyte interface in the circulation process of the lithium ion battery, a generated Solid Electrolyte Interface (SEI) film is damaged, the lithium dendrites can continuously consume the electrolyte in the growth process and cause the irreversible deposition of metal lithium, and the formation of dead lithium causes low coulombic efficiency; the formation of lithium dendrites can even pierce through the separator to cause short circuit inside the lithium ion battery, which causes thermal runaway of the battery to cause combustion explosion.
Due to the unevenness of the surface of the graphite negative electrode of the lithium ion battery, a place and convenience are provided for the formation of lithium dendrites. Lithium dendrites are deposited at the contact part of the diaphragm and the negative electrode, and the growth direction is along the trend from the negative electrode to the diaphragm, so that the lithium dendrites are easy to pierce through the diaphragm substrate in the continuous forming process. For example, in the prior art, the chinese utility model patent with the publication number CN205406613U discloses a soft ceramic lithium ion battery separator, which comprises a polyolefin microporous membrane base layer; the upper surface and/or the lower surface of the polyolefin microporous membrane base layer are/is covered with a soft ceramic layer, and the soft ceramic layer is a boehmite particle layer. The soft ceramic lithium ion battery diaphragm has low hardness, and is easy to pierce a polyolefin microporous membrane base layer by lithium dendrites in the use process, so that the battery is short-circuited and has poor safety.
Disclosure of Invention
The invention aims to provide a high-safety composite coating diaphragm for a lithium ion battery.
The invention also provides a high-safety lithium ion battery.
In order to achieve the above purpose, the technical scheme adopted by the composite coating diaphragm for the lithium ion battery is as follows:
the composite coating membrane for the lithium ion battery comprises a membrane substrate and a composite coating layer arranged on one side of the membrane substrate, wherein the composite coating layer comprises a silica coating layer arranged on the membrane substrate and a first boehmite coating layer arranged on the silica coating layer.
The composite coating of the composite coating diaphragm for the lithium ion battery comprises a silicon dioxide coating and a first boehmite coating; the silica coating is firstly coated on the surface of the diaphragm substrate, and the first boehmite coating is coated on the silica coating. Diaphragm is when preparation electricity core, and composite coating is relative with negative pole active material, and the lithium dendrite that produces at negative pole and electrolyte interface in the battery use can constantly increase, and the following reaction can take place when dendrite and the contact of silica coating:
SiOx+yLi+ye→Si+LiyOx
yLi+SiOx→LiySiOx
Figure BDA0001876139330000021
through the reaction, the growth of the lithium dendrite is restrained to a certain degree, and the problems of performance attenuation and safety caused by the fact that the lithium dendrite penetrates a diaphragm after continuously and rapidly growing are avoided. In addition, the first boehmite coating coated on the surface of the silica coating avoids the reaction of the silica and the metal lithium on the surface of the negative electrode before lithium dendrites appear, so that the excessive loss of the effective lithium of the battery is prevented; and the further growth of the lithium dendrite can be delayed, so that the service life of the battery is effectively prolonged, and the occurrence of battery safety accidents is reduced.
The composite coating diaphragm for the lithium ion battery further comprises a second boehmite coating layer arranged on the other surface of the diaphragm base material. The second boehmite coating layer enables the composite coating membrane to have the comprehensive performance of a conventional ceramic coating membrane. Meanwhile, the existence of the second boehmite coating can balance the surface tension of two sides of the base material, so that the composite coating diaphragm can not have the common heating curling phenomenon of a single-side coated diaphragm in a high-temperature environment, and the possible contact short circuit of a positive pole piece and a negative pole piece is avoided.
The first boehmite coating layer comprises boehmite particles; the particle size of the boehmite particles is 0.1-2.2 μm. Controlling the particle size of the boehmite particles in the first boehmite coating layer within this range enables to avoid clogging of the membrane pore base material while ensuring a bulk density at the time of coating application and to make the thickness controllable.
The thickness of the composite coating is 3-4 mu m; the ratio of the thickness of the silica coating to the thickness of the first boehmite coating is 1:7 to 7: 1. The total thickness of the composite coating and the thicknesses of the silica coating and the first boehmite coating are controlled within the range, so that the safety performance of the pole piece can be improved, and the permeability of lithium ions can be ensured.
The silica coating comprises silica particles; the particle size of the silicon dioxide particles is 0.1-1.2 mu m. The particle size of the silicon dioxide particles in the silicon dioxide coating is controlled in the range, so that the blocking of a diaphragm hole base material can be avoided, the stacking density of the coating during coating can be ensured, and the thickness can be controlled.
The technical scheme adopted by the lithium ion battery is as follows:
a lithium ion battery comprises a battery cell, wherein the battery cell comprises a positive plate, a negative plate and a diaphragm, and the diaphragm is the composite coating diaphragm for the lithium ion battery; the surface of the composite coating diaphragm provided with the composite coating is opposite to the negative plate.
The lithium ion battery has a simple structure and higher safety performance.
Drawings
Fig. 1 is a schematic view of a composite coated separator for a lithium ion battery in example 1 of the composite coated separator for a lithium ion battery according to the present invention, in which 1-a separator substrate, 2-a composite coating layer, 3-a silica coating layer, 4-a first boehmite coating layer, and 5-a second boehmite coating layer.
Detailed Description
The invention provides a composite coating diaphragm for a lithium ion battery, which comprises a diaphragm substrate and a composite coating layer arranged on one surface of the diaphragm substrate, wherein the composite coating layer comprises a silica coating layer arranged on the diaphragm substrate and a first boehmite coating layer arranged on the silica coating layer.
The composite coating diaphragm for the lithium ion battery further comprises a second boehmite coating layer arranged on the other surface of the diaphragm base material.
The first boehmite coating layer comprises boehmite particles; the particle size of the boehmite particles is 0.1-2.2 μm. The mass fraction of boehmite in the first boehmite coating layer is not less than 95.5%.
The second boehmite coating layer comprises boehmite particles; the particle size of the boehmite particles is 0.1-2.2 μm. The mass fraction of boehmite in the second boehmite coating layer is not less than 95.5%.
The thickness of the composite coating is 3-4 mu m; the ratio of the thickness of the silica coating to the thickness of the first boehmite coating is 1:7 to 7: 1.
The silica coating comprises silica particles; the particle size of the silicon dioxide particles is 0.1-1.2 mu m. The mass fraction of silicon dioxide in the silicon dioxide coating is not less than 95.5%.
The technical solution of the present invention will be further described with reference to the following embodiments.
In the embodiment of the composite coating diaphragm for the lithium ion battery, the boehmite slurry adopted in the preparation of the composite coating diaphragm for the lithium ion battery is prepared by adopting the following method: taking raw materials according to the mass ratio of boehmite, a polyvinyl alcohol dispersing agent, an organic silicon defoaming agent and a polystyrene-acrylate emulsion binder for coating the diaphragm of 95.5:1:0.5: 3; adding boehmite, a polyvinyl alcohol dispersing agent and an organic silicon defoaming agent for coating the diaphragm into deionized water, uniformly dispersing the slurry through a premixing-ball milling-high-speed dispersion process, then adding a polystyrene-acrylate emulsion binder, and continuously stirring and dispersing to obtain the boehmite slurry with the solid content of 30%.
In the embodiment of the composite coating diaphragm for the lithium ion battery, the silicon dioxide slurry adopted in the preparation of the composite coating diaphragm for the lithium ion battery is prepared by adopting the following method: taking the raw materials according to the mass ratio of 95.5:1:0.5:3 of silicon dioxide, polyvinyl alcohol dispersant, organic silicon defoamer and polystyrene-acrylate emulsion binder; adding silicon dioxide, a polyvinyl alcohol dispersant and an organic silicon defoamer into deionized water, uniformly dispersing the slurry through a premixing-ball milling-high-speed dispersion process, then adding a polystyrene-acrylate emulsion binder, and continuously stirring and dispersing to obtain the silicon dioxide slurry with the solid content of 30%.
Example 1 of composite coated separator for lithium ion battery
The composite coating diaphragm for the lithium ion battery of the embodiment comprises a diaphragm substrate 1 and a composite coating 2 arranged on one surface of the diaphragm substrate 1, as shown in fig. 1; the composite coating 2 includes a silica coating 3 disposed on the separator substrate 1 and a first boehmite coating 4 disposed on the silica coating 3; the composite coating diaphragm for the lithium ion battery further comprises a second boehmite coating 5 arranged on the other side of the diaphragm substrate 1. The diaphragm base material is an unmodified PE film with the thickness of 9 mu m; the silica coating had a thickness of 2.5 μm and the first boehmite coating had a thickness of 1.0. mu.m. The thickness of the second boehmite coating layer was 3.0 μm. The particle size of the silica in the silica coating layer is 0.1 μm, the particle size of the boehmite in the first boehmite coating layer is 2.2 μm, and the particle size of the boehmite in the second boehmite coating layer is 1.2 μm.
The preparation method of the composite coating diaphragm for the lithium ion battery comprises the following steps: coating silica ceramic slurry on one surface of a diaphragm base material in a gravure roll coating mode, drying to form a silica coating, and coating boehmite slurry on the surface of the silica coating and drying to form a first boehmite coating; and coating the boehmite slurry on the other side of the diaphragm base material, and drying to form a second boehmite coating layer.
Example 2 of composite coating separator for lithium ion battery
The composite coated separator for a lithium ion battery of the present example is different from example 1 of the composite coated separator for a lithium ion battery only in that: the silica coating layer has a thickness of 3.0 μm, the first boehmite coating layer has a thickness of 0.5 μm, the second boehmite coating layer has a thickness of 3.5 μm, the particle size of silica in the silica coating layer is 1.2 μm, the particle size of boehmite in the first boehmite coating layer is 0.1 μm, and the particle size of boehmite in the second boehmite coating layer is 2.2 μm.
The preparation method of the composite coating diaphragm for the lithium ion battery of the embodiment is the same as that of the embodiment 1 of the composite coating diaphragm for the lithium ion battery.
Example 3 of composite coated separator for lithium ion battery
The composite coating diaphragm for the lithium ion battery comprises a diaphragm base material and a composite coating arranged on one surface of the diaphragm; the composite coating includes a silica coating disposed on the membrane substrate and a first boehmite coating disposed on the silica coating; the composite coating diaphragm for the lithium ion battery also comprises a second boehmite coating layer arranged on the other side of the diaphragm substrate. The diaphragm base material is an unmodified PE film with the thickness of 9 mu m; the silica coating layer had a thickness of 2.5 μm, the first boehmite coating layer had a thickness of 1.0 μm, the second boehmite coating layer had a thickness of 3.0 μm, the particle size of silica in the silica coating layer was 1 μm, the particle size of boehmite in the first boehmite coating layer was 1.2 μm, and the particle size of boehmite in the second boehmite coating layer was 0.1 μm.
The preparation method of the composite coating diaphragm for the lithium ion battery comprises the following steps:
taking a conventional 9+3PE commercial diaphragm, wherein the commercial diaphragm comprises a PE diaphragm base material with the thickness of 9 microns and a boehmite coating with the thickness of 3 microns coated on one side of the diaphragm base material, and the other side of the diaphragm base material is not coated; coating silica slurry on the uncoated side of a conventional 9+3PE commodity diaphragm by a gravure roll coating mode, drying to form a silica coating, coating boehmite slurry on the surface of the silica coating, and drying to form a first boehmite coating.
Example 4 of composite coated separator for lithium ion batteries
The composite coating diaphragm for the lithium ion battery comprises a diaphragm base material and a composite coating arranged on one side of the diaphragm, wherein the composite coating comprises a silica coating arranged on the diaphragm base material and a first boehmite coating arranged on the silica coating; the composite coating diaphragm for the lithium ion battery also comprises a second boehmite coating layer arranged on the other side of the diaphragm substrate. The diaphragm base material is an unmodified PP film with the thickness of 12 mu m; the silica coating layer had a thickness of 3.5 μm, the first boehmite coating layer had a thickness of 0.5 μm, the second boehmite coating layer had a thickness of 4.0 μm, the particle size of silica in the silica coating layer was 0.5 μm, and the particle size of boehmite in the first boehmite coating layer was 1.7 μm.
The preparation method of the composite coating diaphragm for the lithium ion battery comprises the following steps:
taking a conventional 12+4PP commercial diaphragm, wherein the commercial diaphragm comprises a PP diaphragm base material with the thickness of 12 microns and a boehmite coating with the thickness of 4 microns coated on one side of the diaphragm base material, and the other side of the diaphragm base material is not coated; coating silica slurry on the uncoated side of a conventional 12+4PP commodity diaphragm by a gravure roll coating mode, drying to form a silica coating, coating boehmite slurry on the surface of the silica coating, and drying to form a first boehmite coating.
Example 5 of composite coated separator for lithium ion battery
The composite coating diaphragm for the lithium ion battery of the embodiment is different from the composite coating diaphragm in the embodiment 4 of the lithium ion battery composite coating diaphragm only in that: the silica coating had a thickness of 3.0 μm and the first boehmite coating had a thickness of 1.0 μm.
The preparation method of the composite coating diaphragm for the lithium ion battery of the embodiment is the same as the preparation method of the composite coating diaphragm for the lithium ion battery of the embodiment 4.
Example 6 of composite coated separator for lithium ion battery
The composite coated separator for a lithium ion battery of the present example is different from the composite coated separator of example 1 of the composite coated separator for a lithium ion battery only in that: the silica coating had a thickness of 2.5 μm and the first boehmite coating had a thickness of 0.5 μm.
Example 7 of composite coated separator for lithium ion battery
The composite coated separator for a lithium ion battery of the present example is different from the composite coated separator of example 1 of the composite coated separator for a lithium ion battery only in that: the silica coating had a thickness of 0.5 μm and the second boehmite coating had a thickness of 3.5 μm.
Example 1 of lithium ion Battery
The lithium ion battery comprises a shell and a battery cell arranged in the shell, wherein the battery cell comprises a positive plate, a diaphragm and a negative plate which are sequentially arranged; the diaphragm adopted is the composite coating diaphragm for the lithium ion battery in the embodiments 1, 3 and 4, and the composite coating of the composite coating diaphragm for the lithium ion battery is opposite to the negative plate.
The preparation method of the battery cell adopted by the lithium ion battery of the embodiment comprises the following steps: the positive plate, the diaphragm and the negative plate are sequentially arranged, the composite coating of the composite coating diaphragm for the lithium ion battery is opposite to the negative plate in the arrangement process, and then the Z-shaped laminated battery core is prepared.
Example 2 of lithium ion Battery
The lithium ion battery comprises a shell and a battery cell arranged in the shell, wherein the battery cell comprises a positive plate, a diaphragm and a negative plate which are sequentially arranged; the diaphragm adopted is the composite coating diaphragm for the lithium ion battery in the embodiments 2, 3 and 5 of the composite coating diaphragm for the lithium ion battery, and the composite coating of the composite coating diaphragm for the lithium ion battery is opposite to the negative plate.
The preparation method of the battery core adopted by the lithium ion battery in the embodiment comprises the following steps: the positive plate, the diaphragm and the negative plate are sequentially arranged, the composite coating of the composite coating diaphragm for the lithium ion battery is opposite to the negative plate in the arrangement process, and then the 'return' type winding battery core is prepared.

Claims (6)

1. The utility model provides a composite coating diaphragm for lithium ion battery which characterized in that: the composite coating comprises a membrane substrate and a composite coating layer arranged on one side of the membrane substrate, wherein the composite coating layer comprises a silica coating layer arranged on the membrane substrate and a first boehmite coating layer arranged on the silica coating layer.
2. The composite coated separator for a lithium ion battery according to claim 1, wherein: the composite coating diaphragm for the lithium ion battery further comprises a second boehmite coating layer arranged on the other surface of the diaphragm base material.
3. The composite coated separator for a lithium ion battery according to claim 1, wherein: the first boehmite coating layer comprises boehmite particles; the particle size of the boehmite particles is 0.1-2.2 μm.
4. The composite coating separator for a lithium ion battery according to any one of claims 1 to 3, characterized in that: the thickness of the composite coating is 3-4 mu m; the ratio of the thickness of the silica coating to the thickness of the first boehmite coating is 1:7 to 7: 1.
5. The composite coating separator for a lithium ion battery according to any one of claims 1 to 3, characterized in that: the silica coating comprises silica particles; the particle size of the silicon dioxide particles is 0.1-1.2 mu m.
6. The utility model provides a lithium ion battery, includes electric core, electric core includes positive plate, negative pole piece and diaphragm, its characterized in that: the separator is the composite coating separator for the lithium ion battery according to claim 1; the surface of the composite coating diaphragm provided with the composite coating is opposite to the negative plate.
CN201811400131.3A 2018-11-22 2018-11-22 Composite coating diaphragm for lithium ion battery and lithium ion battery Pending CN111211278A (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103915591A (en) * 2014-04-09 2014-07-09 深圳市星源材质科技股份有限公司 Water-based ceramic coating lithium ion battery diaphragm and processing method thereof
WO2016159720A1 (en) * 2015-04-02 2016-10-06 에스케이이노베이션 주식회사 Composite separation membrane for lithium secondary battery and manufacturing method therefor
CN205810930U (en) * 2016-07-05 2016-12-14 东莞市卓高电子科技有限公司 The lithium battery diaphragm of improvement
CN106981607A (en) * 2016-01-19 2017-07-25 中国电力科学研究院 A kind of lithium ion battery separator and preparation method thereof
CN207765523U (en) * 2017-12-28 2018-08-24 东莞市赛洋新能源科技有限公司 A kind of diaphragm and the lithium battery with the diaphragm

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103915591A (en) * 2014-04-09 2014-07-09 深圳市星源材质科技股份有限公司 Water-based ceramic coating lithium ion battery diaphragm and processing method thereof
WO2016159720A1 (en) * 2015-04-02 2016-10-06 에스케이이노베이션 주식회사 Composite separation membrane for lithium secondary battery and manufacturing method therefor
CN106981607A (en) * 2016-01-19 2017-07-25 中国电力科学研究院 A kind of lithium ion battery separator and preparation method thereof
WO2017124715A1 (en) * 2016-01-19 2017-07-27 中国电力科学研究 Lithium-ion battery separator and preparation method therefor
CN205810930U (en) * 2016-07-05 2016-12-14 东莞市卓高电子科技有限公司 The lithium battery diaphragm of improvement
CN207765523U (en) * 2017-12-28 2018-08-24 东莞市赛洋新能源科技有限公司 A kind of diaphragm and the lithium battery with the diaphragm

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