CN104993082A - Preparation method for nano-alumina particle modified ceramic diaphragm - Google Patents

Preparation method for nano-alumina particle modified ceramic diaphragm Download PDF

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Publication number
CN104993082A
CN104993082A CN201510291767.9A CN201510291767A CN104993082A CN 104993082 A CN104993082 A CN 104993082A CN 201510291767 A CN201510291767 A CN 201510291767A CN 104993082 A CN104993082 A CN 104993082A
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ceramic diaphragm
diaphragm
preparation
alumina particles
lithium
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CN201510291767.9A
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丁建宁
郑祥
刘振
袁宁一
仲玉娇
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Changzhou University
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Changzhou University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/403—Manufacturing processes of separators, membranes or diaphragms
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Nanotechnology (AREA)
  • Electrochemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Composite Materials (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Materials Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Secondary Cells (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Cell Separators (AREA)

Abstract

The invention relates to lithium-sulfur battery diaphragms, in particular to a preparation method for a nano-alumina particle modified ceramic diaphragm. The method includes: firstly weighing certain mass Al2O3 and an adhesive in a mortar; then weighing N-methyl pyrrolidone and adding it into the mortar, and grinding the material uniformly; coating a conventional high polymer diaphragm with the ground nano-alumina particles, and putting the diaphragm into a drying oven to conduct drying. According to the invention, by coating the conventional high polymer diaphragm with a layer of thin nano Al2O3 particle ceramic membrane, the problem that conventional high polymer diaphragms are easy to pierce can be eased, thereby improving battery performance, improving the discharge rate of batteries, significantly prolonging the cycle period of lithium-sulfur batteries, and improving the high temperature resistance and safety of lithium ion batteries. And the ceramic coated special diaphragm is especially suitable for power batteries.

Description

The preparation method of the ceramic diaphragm that a kind of nano alumina particles is modified
Technical field
The present invention relates to lithium-sulfur cell barrier film, mainly a kind of Al that can bear certain mechanical strength 2o 3ceramic diaphragm, belongs to lithium-sulfur cell diaphragm material modification field.
Background technology
At present, the barrier film that lithium-sulfur cell is mainly applied has the polymer separators such as polyethylene (PE) and polypropylene (PP), and in charge and discharge process, the dissolving repeatedly of lithium metal and deposition, easily form Li dendrite, and Li dendrite easily comes off from pole plate, causes battery capacity to reduce; If Li dendrite grows gradually, then can pierce through barrier film and extend to positive pole and cause internal short-circuit, cause the unsafe factor such as fire or blast, this is also the reason that existing lithium-sulfur cell technology is difficult to large-scale commercial application.For this reason, the present invention proposes to utilize nano alumina particles to modify and prepares a kind of ceramic diaphragm, compared with the polymer separators such as PE or PP conventional in lithium ion battery, and Al 2o 3ceramic diaphragm has certain mechanical strength, can extend the life cycle of battery significantly, improves the fail safe of battery.And be specially adapted to electrokinetic cell.
Summary of the invention
Easily being pierced for solving polymer separators the problem causing battery short circuit, the invention provides a kind of ceramic diaphragm of decorated nanometer alumina particle on conventional PE barrier film, PP and PE composite diaphragm.
According to an embodiment of the present invention, a kind of lithium-sulfur cell, comprise sulfur electrode, metal lithium electrode and the barrier film be placed between described sulfur electrode and metal lithium electrode and electrolyte, wherein, described barrier film is the Al made by coating processes 2o 3ceramic diaphragm.
According to an embodiment of the present invention, described lithium-sulfur cell Al 2o 3barrier film, is characterized in that: described Al 2o 3ceramic diaphragm is by grinding, coating, stoving process preparation, and concrete steps are as follows:
(1) nanometer Al is taken 2o 3particle and binding agent are in mortar.
(2) measuring 1-METHYLPYRROLIDONE adds in mortar, and then grinding evenly.
(3) material after grinding is evenly coated on the composite diaphragm of PE barrier film or PP and PE, and takes out after barrier film is put into oven for drying, both obtained ceramic diaphragm.
Described Al 2o 3the particle diameter of powder is less than 100 nm.
The addition of described 1-METHYLPYRROLIDONE is calculated as follows: the Al of every 100 mg 2o 31 ~ 2 milliliter is dripped with PVDF.
Described coated with nano Al 2o 3the amount of particle is depending on the capacity of sulfur electrode, and 10 mAh are about 5 ~ 10 mg/cm 2, but capacity is not directly proportional to ceramic diaphragm thickness.
Described oven dry refers to continue 30 ~ 50 min in 50 ~ 80 DEG C.
According to an embodiment of the present invention, the Al of described lithium-sulfur cell 2o 3barrier film, is characterized in that: described Al 2o 3ceramic diaphragm coating is by Al 2o 3with adhesive mixture by a certain percentage, then add 1-METHYLPYRROLIDONE and grind.
According to an embodiment of the present invention, described lithium-sulfur cell Al 2o 3barrier film, is characterized in that: adhesive used is Kynoar, the one in polyacrylic acid and sodium carboxymethylcellulose.
According to an embodiment of the present invention, described lithium-sulfur cell Al 2o 3barrier film, is characterized in that: the dripping quantity of 1-METHYLPYRROLIDONE used, works as Al 2o 31 ~ 2 milliliter of 1-METHYLPYRROLIDONE is dripped when being 100 mg with adhesive gross mass.
According to an embodiment of the present invention, described lithium-sulfur cell Al 2o 3barrier film, is characterized in that: adhesive therefor accounts for Al 2o 3be 1 ~ 20%, Al with the ratio of binding agent gross mass 2o 3account for 80 ~ 99%.
According to an embodiment of the present invention, described lithium-sulfur cell Al 2o 3barrier film, is characterized in that: Al on conventional polymer separators 2o 3coated weight is 5 ~ 10 mg/cm 2.
According to an embodiment of the present invention, described lithium-sulfur cell Al 2o 3barrier film, is characterized in that: oven temperature controls at 50 ~ 80 DEG C, drying time 30 ~ 50 min.
The invention provides and prepare lithium-sulfur cell Al based on paint-on technique 2o 3the technique of barrier film, by substituting the method for traditional polymer separators with ceramic diaphragm, improves cycle period and the fail safe of battery, thus solution sulphur lithium battery diaphragm is easily pierced through by Li dendrite and causes the problem of cell damage.And, at Al 2o 3with different ratios can be selected in the ratio of PVDF to match, thus affect the performance of lithium-sulfur cell to some extent.
Ceramic diaphragm is to the performance requirement of aluminium oxide: particle size uniformity, can well bond on barrier film, can not block membrane pore size again; Aluminium oxide purity is high, can not introduce impurity, affect cell internal environment; The requirement of aluminium oxide crystalline structure, ensures that aluminium oxide is to the compatibility of electrolyte and wettability.
The present invention prepares Al 2o 3the compression strength of barrier film is better, and Al 2o 3cost low, be suitable for doing the features such as coating material; Al prepared by the present invention 2o 3the lithium-sulfur cell performance test of barrier film, with the method for this area routine, is namely assembled into button half-cell or full battery carries out charge-discharge test investigation.
Accompanying drawing explanation
The composite diaphragm of Fig. 1 to be thickness be PP and PE of 38 micron thickness.
Fig. 2 is coated nanometer Al in example 1 2o 3the ceramic diaphragm of particle.
Fig. 3 is coated nanometer Al in example 2 2o 3the ceramic diaphragm of particle.
Cycle-index-discharge capacity the curve chart of the composite diaphragm assembling button cell of Fig. 4 to be thickness be 38 microns of PP and PE.
Fig. 5 is the cycle-index-discharge capacity curve chart of ceramic diaphragm assembling button cell in example 1.
Fig. 6 is the cycle-index-discharge capacity curve chart of ceramic diaphragm assembling button cell in example 2.
Embodiment
Below, a kind of based on Al to the present invention in conjunction with embodiment 2o 3lithium-sulfur cell of ceramic diaphragm and preparation method thereof elaborates.
Al in embodiments of the present invention 2o 3for nanometer materials, than other nano material, Al 2o 3high, the fabulous dispersion of even particle size distribution, purity, its specific surface is high, has resistant to elevated temperatures inertia, high activity, belongs to activated alumina; Porousness; Hardness is high, good stability of the dimension.
In embodiments of the present invention, described Al 2o 3ceramic diaphragm, its preparation method is cladding process.
embodiment 1 nanometer Al 2 o 3 the preparation of the ceramic diaphragm of particle modification
Be 200-300 object Al by the particle diameter of 100 milligrams 2o 3particle, binding agent mixes according to a certain percentage and adds 1 milliliter of 1-METHYLPYRROLIDONE grinding prepares coating material; Wherein, adhesive is Kynoar (PVDF), at Al 2o 3be 6% with the ratio in the gross mass of PVDF; Al 2o 3account for 94%.
Mixture after ground is coated in 10 square centimeters equably, thickness be PP and the PE of 38 microns composite diaphragm on (Fig. 1), coated weight is 5 ~ 10 mg/cm 2.
Coated barrier film is placed in 70 DEG C of baking ovens, takes out after 50min, obtain ceramic diaphragm.Diaphragm material after coating is as Fig. 2.
embodiment 2 nanometer Al 2 o 3 the preparation of the ceramic diaphragm of particle modification
Be 200-300 object Al by the particle diameter of 300 milligrams 2o 3particle, binding agent mixes according to a certain percentage and adds 3 milliliters of 1-METHYLPYRROLIDONE grindings prepares coating material; Wherein, adhesive is Kynoar (PVDF), at Al 2o 3be 10% with the ratio in the gross mass of PVDF; Al 2o 3account for 90%.
Mixture after ground is coated in 10 square centimeters equably, and thickness is on the PE barrier film of 25 microns, and coated weight is 20 ~ 25 mg/cm 2.
Coated barrier film is placed in 70 DEG C of baking ovens, takes out after 50min, obtain ceramic diaphragm.Diaphragm material after coating is as Fig. 3.
the performance test of embodiment 3 lithium-sulfur cell
Get the Al of composite diaphragm that thickness is PP and the PE of 38 microns and embodiment 1,2 2o 3ceramic diaphragm, is assembled into button cell respectively and carries out charge-discharge test, and the cycle-index-discharge capacity curve chart of barrier film assembling button cell is followed successively by Fig. 4, Fig. 5, Fig. 6.
According to the cycle-index-discharge capacity curve of Fig. 4, discharging current is 2mA, can obviously find out, initial discharge capacity is about 13 mAh, along with constantly carrying out of discharge and recharge, the capacity of second circulation slightly reduces, this is mainly because polysulfide loses in the solution, cause the loss of discharge capacity of the cell, along with the carrying out of circulation, put a capacity to stablize gradually, but because the capacity of lithium-sulfur cell is higher, and discharging current is larger, for the continuous consumption of lithium an-ode, the generation of Li dendrite also constantly aggravates, cause piercing through of barrier film, battery short circuit, as shown in Figure 4, at the 25th circulation time, battery short circuit.
According to the cycle-index-discharge capacity curve of Fig. 5, discharging current is 3 mA, can find out, initial capacity is about 14 mAh, along with the carrying out of discharge and recharge, in front 2 ~ 3 circulations, discharge capacity declines comparatively violent, main cause is the absorption of alumina particle to polysulfide, the loss of polysulfide causes the loss in sulphur source in lithium-sulfur cell, directly decreases the capacity of lithium-sulfur cell, but, relative to the lithium-sulfur cell of high power capacity, the loss of polysulfide can be ignored relatively, and the cyclical stability of battery can significantly improve, and illustrates and adopts Al 2o 3the method that high power capacity lithium-sulfur cell prepared by pottery modification barrier film is feasible.
According to the cycle-index-discharge capacity curve of Fig. 6, discharging current is 3 mA, can see and eat, initial capacity is about 13.5 mAh, in front 10 circulations, discharge capacity declines comparatively violent, and main cause main cause is the absorption of alumina particle to polysulfide, and the loss of polysulfide causes the loss in sulphur source in lithium-sulfur cell, directly decrease the capacity of lithium-sulfur cell, after 15 circulations, discharge capacity is stabilized in about 10 mAh.
According to the curve comparison figure of the cycle-index-discharge capacity of Fig. 4 ~ 6, absolutely prove Al 2o 3the method that high power capacity lithium-sulfur cell prepared by pottery modification barrier film is feasible.According to the contrast of Fig. 5 and Fig. 6, can find, when capacity is similar, nanometer Al 2o 3the ceramic diaphragm of particle modification is thicker, and capacitance loss is relatively many, thus when capacity is certain, and nanometer Al 2o 3the ceramic diaphragm of particle modification is comparatively large to the performance impact of lithium-sulfur cell, needs the capacity of matching battery, adopts the Al of optimum thickness 2o 3pottery is modified barrier film and is prepared high power capacity lithium-sulfur cell.

Claims (7)

1. a preparation method for the ceramic diaphragm of nano alumina particles modification, is characterized in that concrete steps are as follows:
(1) Al is taken 2o 3powder and binding agent are in mortar;
(2) measuring 1-METHYLPYRROLIDONE adds in mortar, and then grinding evenly;
(3) material after grinding is evenly coated on the composite diaphragm of polythene PE barrier film or polypropylene PP and polythene PE, and takes out after barrier film is put into oven for drying, obtain ceramic diaphragm.
2. the preparation method of the ceramic diaphragm of a kind of nano alumina particles modification as claimed in claim 1, is characterized in that: described Al 2o 3the particle diameter of particle is less than 100 nm.
3. the preparation method of the ceramic diaphragm of a kind of nano alumina particles modification as claimed in claim 1, is characterized in that: the addition of described 1-METHYLPYRROLIDONE is calculated as follows: the Al of every 100 mg 2o 31 ~ 2 milliliter of 1-METHYLPYRROLIDONE is dripped with in binding agent.
4. the preparation method of ceramic diaphragm that modifies of a kind of nano alumina particles as claimed in claim 1, is characterized in that: the amount of the nano alumina particles of described coating is depending on the capacity of sulfur electrode, and 10 mAh are 5 ~ 10 mg/cm 2, but capacity is not directly proportional to ceramic diaphragm thickness.
5. the preparation method of the ceramic diaphragm of a kind of nano alumina particles modification as claimed in claim 1, is characterized in that: described oven dry refers to continue 30 ~ 50 min in 50 ~ 80 DEG C.
6. the preparation method of ceramic diaphragm that modifies of a kind of nano alumina particles as claimed in claim 1, is characterized in that: described adhesive is Kynoar, the one in polyacrylic acid and sodium carboxymethylcellulose.
7. the preparation method of the ceramic diaphragm of a kind of nano alumina particles modification as claimed in claim 1, is characterized in that: described adhesive accounts for Al 2o 3be 1 ~ 20%, Al with the ratio of binding agent gross mass 2o 3account for 80 ~ 99%.
CN201510291767.9A 2015-06-01 2015-06-01 Preparation method for nano-alumina particle modified ceramic diaphragm Pending CN104993082A (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106920919A (en) * 2017-01-23 2017-07-04 浙江钱江锂电科技有限公司 A kind of stacked soft-package battery
CN107285352A (en) * 2017-06-13 2017-10-24 深圳市雄韬电源科技股份有限公司 The preparation method and applications of nano aluminium oxide
CN108428839A (en) * 2018-03-06 2018-08-21 华南师范大学 A kind of covalent organic frame coated separator and its preparation method and application
CN112909434A (en) * 2019-11-18 2021-06-04 青岛蓝科途膜材料有限公司 Lithium ion battery diaphragm and preparation method thereof and lithium ion battery
US11264677B2 (en) 2018-06-06 2022-03-01 Ningde Amperex Technology Limited Separator and electrochemical device

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101814590A (en) * 2010-04-23 2010-08-25 湖南业翔晶科新能源有限公司 Porous solid membrane used for lithium ion battery and production method thereof
CN102244223A (en) * 2011-05-26 2011-11-16 东莞新能源科技有限公司 Electrochemical device and inorganic/organic composite porous membrane
CN102299285A (en) * 2011-07-25 2011-12-28 华南理工大学 Porous inorganic membrane used for lithium ion battery diaphragm and preparation method thereof
CN103390741A (en) * 2013-07-26 2013-11-13 常州大学 Diaphragm of organic/inorganic composite porous coating, and preparation method of diaphragm
US20150037651A1 (en) * 2013-07-31 2015-02-05 GM Global Technology Operations LLC Porous composite structures for lithium-ion battery separators

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101814590A (en) * 2010-04-23 2010-08-25 湖南业翔晶科新能源有限公司 Porous solid membrane used for lithium ion battery and production method thereof
CN102244223A (en) * 2011-05-26 2011-11-16 东莞新能源科技有限公司 Electrochemical device and inorganic/organic composite porous membrane
CN102299285A (en) * 2011-07-25 2011-12-28 华南理工大学 Porous inorganic membrane used for lithium ion battery diaphragm and preparation method thereof
CN103390741A (en) * 2013-07-26 2013-11-13 常州大学 Diaphragm of organic/inorganic composite porous coating, and preparation method of diaphragm
US20150037651A1 (en) * 2013-07-31 2015-02-05 GM Global Technology Operations LLC Porous composite structures for lithium-ion battery separators

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106920919A (en) * 2017-01-23 2017-07-04 浙江钱江锂电科技有限公司 A kind of stacked soft-package battery
CN107285352A (en) * 2017-06-13 2017-10-24 深圳市雄韬电源科技股份有限公司 The preparation method and applications of nano aluminium oxide
CN108428839A (en) * 2018-03-06 2018-08-21 华南师范大学 A kind of covalent organic frame coated separator and its preparation method and application
US11264677B2 (en) 2018-06-06 2022-03-01 Ningde Amperex Technology Limited Separator and electrochemical device
CN112909434A (en) * 2019-11-18 2021-06-04 青岛蓝科途膜材料有限公司 Lithium ion battery diaphragm and preparation method thereof and lithium ion battery

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Application publication date: 20151021