CN111477818B - Full-ceramic lithium ion battery diaphragm and preparation method thereof - Google Patents

Full-ceramic lithium ion battery diaphragm and preparation method thereof Download PDF

Info

Publication number
CN111477818B
CN111477818B CN202010332682.1A CN202010332682A CN111477818B CN 111477818 B CN111477818 B CN 111477818B CN 202010332682 A CN202010332682 A CN 202010332682A CN 111477818 B CN111477818 B CN 111477818B
Authority
CN
China
Prior art keywords
lithium ion
ion battery
diaphragm
ceramic
battery diaphragm
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202010332682.1A
Other languages
Chinese (zh)
Other versions
CN111477818A (en
Inventor
薛兵
李晔
李冬妮
杨阔
李芳菲
雒锋
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Jilin University
Original Assignee
Jilin University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Jilin University filed Critical Jilin University
Priority to CN202010332682.1A priority Critical patent/CN111477818B/en
Publication of CN111477818A publication Critical patent/CN111477818A/en
Application granted granted Critical
Publication of CN111477818B publication Critical patent/CN111477818B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/403—Manufacturing processes of separators, membranes or diaphragms
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/431—Inorganic material
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Cell Separators (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Secondary Cells (AREA)

Abstract

The invention relates to an all-ceramic lithium ion battery diaphragm and a preparation method thereof, belonging to the field of diaphragm materials. The method takes diatomite as a main raw material, is matched with lithium hydroxide, is doped with a small amount of rare earth elements, is formed by using an organic binder, and forms the all-ceramic lithium ion battery diaphragm taking silicon dioxide and lithium silicate as main components after high-temperature calcination. The diaphragm has excellent thermal stability, and thoroughly solves the safety problem that the traditional lithium ion battery diaphragm is heated to shrink and deform so as to cause the internal short circuit of the battery to cause fire. Meanwhile, the diaphragm has the characteristics of good electrolyte affinity, high porosity and large liquid absorption amount, effectively promotes the mass transfer efficiency of lithium ions in the battery, and improves the capacity retention rate of the battery in large-current charging and discharging and long-time operation.

Description

Full-ceramic lithium ion battery diaphragm and preparation method thereof
Technical Field
The invention belongs to the technical field of lithium ion battery diaphragms, and relates to a high-temperature-resistant power type lithium ion battery diaphragm suitable for large-current charging and discharging and a preparation method thereof.
Background art:
the development of electric automobiles puts higher demands on power type lithium ion batteries, and the diaphragm material which is an important component of the lithium ion batteries has important influence on the usability and safety of the batteries. At present, commercial lithium ion battery separator materials are mainly porous polyolefin such as Polyethylene (PE), polypropylene/polyethylene (PP/PE) films and the like, and although polyolefin separators have various advantages when used in lithium ion batteries, the polyolefin separators have the problems of low porosity, poor wettability to electrolyte and the like, and are not favorable for large-current charge and discharge and long-time use capacity maintenance of power batteries. Meanwhile, the polyolefin film has the defects of large high-temperature shrinkage rate and low thermal stability, which are main reasons for high-temperature thermal failure of the battery and short circuit and fire in the battery. Therefore, the development of a novel power type lithium ion battery diaphragm product which is resistant to high temperature and suitable for large-current charging and discharging is an urgent task for developing electric vehicles.
Inorganic ceramic particles, such as boehmite, alumina, silica, titania, zirconia, etc., are selected as a coating material of a polyolefin separator due to excellent thermal stability and electrolyte wettability, to improve thermal stability of the polyolefin separator. For example, patent CN201611228378.2 reports that the thermal stability, puncture resistance and tensile strength of the prepared coating type diaphragm are obviously improved by using polyolefin microporous membrane as a matrix and alumina as a coating. On the basis, patent CN201710533227.6 reports a technology of coating ceramic slurry on both sides of a base film, which effectively avoids the problem of high-temperature curling of a coating type diaphragm, so that the battery diaphragm obtains lower shrinkage rate, and the battery safety is improved. With the advance of the technology, composite separators with multilayer structures have appeared in succession, such as lithium ion battery separators reported in patent CN201911140350.7, which are composed of a polymer base material, a heat-resistant composite functional layer composed of a nano-ceramic material and an aramid polymer, and a polyvinylidene fluoride protective layer. In the aspect of ceramic coating technology, electrostatic spinning mode reported by patent CN201911071686.2 and ceramic material physical vapor deposition technology reported by patent CN201510292908.9 appear. In addition, in order to eliminate the restriction of the polymer base film on the thermal stability of the material, patent CN201810688460.6 does not use the polymer material as a coating base film, and directly coats ceramic slurry formed by mixing ceramic particles and an adhesive on the surface of the positive electrode plate, thereby realizing the integration of the positive electrode diaphragm of the lithium ion battery, and further improving the safety of the battery. However, the polymer binder in the ceramic coating also has the defect of easy shrinkage and decomposition at high temperature, which is a negative factor influencing the thermal stability of the diaphragm. Therefore, the development of the diaphragm material made of all ceramic materials is an effective measure for improving the thermal stability of the lithium ion battery.
The invention content is as follows:
the invention aims to eliminate potential safety hazards of a battery caused by poor thermal stability of a lithium ion battery diaphragm and improve the capacity retention rate of the battery in large-current charging and discharging and long-time operation. Therefore, the natural porous mineral diatomite is used as a main raw material, lithium hydroxide is matched, a small amount of rare earth elements are doped, the natural porous mineral diatomite is formed by using an organic binder, and the natural porous mineral diatomite is calcined at high temperature to form the porous ceramic diaphragm taking silicon dioxide and lithium silicate as main components.
The purpose of the invention is realized by the following technical scheme:
evenly mixing the diatomite, the lithium hydroxide, the rare earth oxide, the binder and the distilled water according to a certain proportion, carrying out compression molding, drying for 4 hours at 80 ℃, calcining to 580 ℃ in a muffle furnace, and carrying out heat preservation for 4-6 hours at the heating rate of 7-9 ℃/min; soaking the obtained calcined sample in 0.05mol/L hydrochloric acid for 10 minutes, washing the calcined sample to be neutral by using distilled water, and drying the calcined sample for 8 hours at the temperature of 100 ℃ to obtain the all-ceramic lithium ion battery diaphragm; the rare earth oxide is lanthanum oxide or cerium oxide; the binder is one of methylcellulose, hydroxypropyl methylcellulose, hydroxyethyl cellulose and carboxymethyl cellulose; the mass ratio of the diatomite to the lithium hydroxide to the rare earth oxide to the binder to the distilled water is 88: 7: 0.1-0.3: 0.2-0.4: 4.5; the diatomite has a silica content greater than 90%.
Has the advantages that: according to the invention, diatomite is used as a main raw material, and a ceramic morphology with a developed pore structure is formed in a calcined product by virtue of a porous structure of the diatomite, so that the diatomite is beneficial to rapid transmission of lithium ions in a large-current charging and discharging process. The porous lithium silicate generated by the reaction of the lithium hydroxide and the silicon dioxide in the diatomite can promote the dissociation of lithium salt in the lithium ion battery electrolyte, promote the lithium ion transmission and improve the multiplying power and the cycle performance of the battery. The use of small amounts of rare earth elements is intended to adjust the electrochemical properties of lithium silicate. The diaphragm obtained by the invention does not contain any organic component, and the inorganic component of the diaphragm is stable at high temperature and is not decomposed, so that the thermal stability temperature of the all-ceramic diaphragm is higher than 700 ℃, and the safety problem of internal short circuit of the battery caused by shrinkage deformation of the lithium ion battery diaphragm due to heating is thoroughly solved. In addition, the all-ceramic diaphragm has high porosity and good electrolyte wettability, so that the mass transfer efficiency of lithium ions in the battery is effectively promoted, and the capacity retention rate of the battery in large-current charging and discharging and long-time operation is improved.
Description of the drawings:
FIG. 1 is a scanning electron microscope photograph of a full ceramic lithium ion battery diaphragm
FIG. 2 shows the rate capability curve of a lithium ion battery using a fully ceramic separator
The specific implementation mode is as follows:
the present invention will be described in further detail with reference to examples:
diatomite, lithium hydroxide, lanthanum oxide (or cerium oxide), a binder (one of methyl cellulose, hydroxypropyl methyl cellulose, hydroxyethyl cellulose and carboxymethyl cellulose), distilled water and the following components in a mass ratio of 88: 7: 0.1-0.3: 0.2-0.4: 4.5, uniformly mixing, carrying out compression molding, drying for 4 hours at 80 ℃, calcining in a muffle furnace to 580 ℃ at 500 ℃ and keeping the temperature for 4-6 hours, wherein the heating rate is 7-9 ℃/min; and soaking the obtained calcined sample in 0.05mol/L hydrochloric acid for 10 minutes, washing the calcined sample to be neutral by using distilled water, and drying the calcined sample for 8 hours at the temperature of 100 ℃ to obtain the all-ceramic lithium ion battery diaphragm.
Example 1
Diatomite, lithium hydroxide, lanthanum oxide, methyl cellulose and distilled water according to the mass ratio of 88: 7: 0.1: 0.4: 4.5, uniformly mixing, carrying out compression molding, drying for 4 hours at 80 ℃, calcining to 500 ℃ in a muffle furnace, and keeping the temperature for 6 hours at the heating rate of 9 ℃/min; and soaking the obtained calcined sample in 0.05mol/L hydrochloric acid for 10 minutes, washing the calcined sample to be neutral by using distilled water, and drying the calcined sample for 8 hours at the temperature of 100 ℃ to obtain the all-ceramic lithium ion battery diaphragm.
The porosity of the full-ceramic lithium ion battery diaphragm is 53.5%, the liquid absorption rate is 179%, and the discharge specific capacity under 10C multiplying power is 92.9mAh g-1(lithium iron phosphate battery system).
Example 2
Diatomite, lithium hydroxide, lanthanum oxide, hydroxypropyl methyl cellulose and distilled water according to the mass ratio of 88: 7: 0.2: 0.3: 4.5, uniformly mixing, carrying out compression molding, drying for 4 hours at 80 ℃, calcining to 520 ℃ in a muffle furnace, and keeping the temperature for 5 hours at the heating rate of 8 ℃/min; and soaking the obtained calcined sample in 0.05mol/L hydrochloric acid for 10 minutes, washing the calcined sample to be neutral by using distilled water, and drying the calcined sample for 8 hours at the temperature of 100 ℃ to obtain the all-ceramic lithium ion battery diaphragm.
The porosity of the full-ceramic lithium ion battery diaphragm is 51.4%, the liquid absorption rate is 168%, and the discharge specific capacity under 10C multiplying power is 90.1mAh g-1(lithium iron phosphate battery system).
Example 3
Diatomite, lithium hydroxide, cerium oxide, hydroxyethyl cellulose and distilled water according to the mass ratio of 88: 7: 0.3: 0.2: 4.5, uniformly mixing, carrying out compression molding, drying for 4 hours at 80 ℃, calcining to 540 ℃ in a muffle furnace, and keeping the temperature for 4 hours at the heating rate of 7 ℃/min; and soaking the obtained calcined sample in 0.05mol/L hydrochloric acid for 10 minutes, washing the calcined sample to be neutral by using distilled water, and drying the calcined sample for 8 hours at the temperature of 100 ℃ to obtain the all-ceramic lithium ion battery diaphragm.
The porosity of the full-ceramic lithium ion battery diaphragm is 54.6%, the liquid absorption rate is 189.0%, and the discharge specific capacity under 10C multiplying power is 96.6mAh g-1(lithium iron phosphate battery system).
Example 4
Diatomite, lithium hydroxide, cerium oxide, carboxymethyl cellulose and distilled water according to the mass ratio of 88: 7: 0.3: 0.2: 4.5, uniformly mixing, carrying out compression molding, drying for 4 hours at 80 ℃, calcining to 580 ℃ in a muffle furnace, and keeping the temperature for 4 hours at the heating rate of 7 ℃/min; and soaking the obtained calcined sample in 0.05mol/L hydrochloric acid for 10 minutes, washing the calcined sample to be neutral by using distilled water, and drying the calcined sample for 8 hours at the temperature of 100 ℃ to obtain the all-ceramic lithium ion battery diaphragm.
The porosity of the full-ceramic lithium ion battery diaphragm is 53.9%, the liquid absorption rate is 179.1%, and the discharge specific capacity under 10C multiplying power is 92.9mAh g-1(lithium iron phosphate battery system).

Claims (3)

1. A preparation method of an all-ceramic lithium ion battery diaphragm is characterized by comprising the following steps:
evenly mixing the diatomite, the lithium hydroxide, the rare earth oxide, the binder and the distilled water according to a certain proportion, carrying out compression molding, drying for 4 hours at 80 ℃, calcining to 580 ℃ in a muffle furnace, and carrying out heat preservation for 4-6 hours at the heating rate of 7-9 ℃/min; soaking the obtained calcined sample in 0.05mol/L hydrochloric acid for 10 minutes, washing the calcined sample to be neutral by using distilled water, and drying the calcined sample for 8 hours at the temperature of 100 ℃ to obtain the all-ceramic lithium ion battery diaphragm; the rare earth oxide is lanthanum oxide or cerium oxide; the binder is one of methylcellulose, hydroxypropyl methylcellulose, hydroxyethyl cellulose and carboxymethyl cellulose; the mass ratio of the diatomite to the lithium hydroxide to the rare earth oxide to the binder to the distilled water is 88: 7: 0.1-0.3: 0.2-0.4: 4.5.
2. the preparation method of the all-ceramic lithium ion battery separator according to claim 1, characterized in that: the diatomite has a silica content greater than 90%.
3. The full-ceramic lithium ion battery diaphragm is characterized in that: obtainable by the process according to any one of claims 1-2.
CN202010332682.1A 2020-04-24 2020-04-24 Full-ceramic lithium ion battery diaphragm and preparation method thereof Active CN111477818B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202010332682.1A CN111477818B (en) 2020-04-24 2020-04-24 Full-ceramic lithium ion battery diaphragm and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202010332682.1A CN111477818B (en) 2020-04-24 2020-04-24 Full-ceramic lithium ion battery diaphragm and preparation method thereof

Publications (2)

Publication Number Publication Date
CN111477818A CN111477818A (en) 2020-07-31
CN111477818B true CN111477818B (en) 2021-04-20

Family

ID=71764059

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010332682.1A Active CN111477818B (en) 2020-04-24 2020-04-24 Full-ceramic lithium ion battery diaphragm and preparation method thereof

Country Status (1)

Country Link
CN (1) CN111477818B (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111952519B (en) * 2020-08-12 2022-04-29 苏州捷力新能源材料有限公司 Ceramic diaphragm and preparation method thereof
CN112490580A (en) * 2020-10-23 2021-03-12 河北金力新能源科技股份有限公司 High-temperature-resistant diaphragm for lithium battery and preparation method thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109285983A (en) * 2018-09-28 2019-01-29 东北大学 Using lithium ion solid electrolyte piece as button lithium battery of diaphragm and preparation method thereof
CN110165294A (en) * 2019-05-31 2019-08-23 浙江国能锂业股份有限公司 A kind of preparation method of highly conductive lithium ion solid electrolyte
CN110931689A (en) * 2019-10-29 2020-03-27 东北大学 Perovskite type lithium ion solid electrolyte diaphragm and preparation and use methods thereof

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100659851B1 (en) * 2005-04-27 2006-12-19 삼성에스디아이 주식회사 Lithium secondary battery

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109285983A (en) * 2018-09-28 2019-01-29 东北大学 Using lithium ion solid electrolyte piece as button lithium battery of diaphragm and preparation method thereof
CN110165294A (en) * 2019-05-31 2019-08-23 浙江国能锂业股份有限公司 A kind of preparation method of highly conductive lithium ion solid electrolyte
CN110931689A (en) * 2019-10-29 2020-03-27 东北大学 Perovskite type lithium ion solid electrolyte diaphragm and preparation and use methods thereof

Also Published As

Publication number Publication date
CN111477818A (en) 2020-07-31

Similar Documents

Publication Publication Date Title
US20240055724A1 (en) Composite separator and preparation method therefor and use thereof
CN111653717B (en) Preparation method of composite diaphragm, composite diaphragm and lithium ion battery
CN110970668B (en) All-solid-state battery composite structure, preparation method and application thereof
CN107611314B (en) Lithium ion battery and coating diaphragm thereof
CN110707267B (en) Composite diaphragm for alkali metal battery and preparation and application thereof
CN111477818B (en) Full-ceramic lithium ion battery diaphragm and preparation method thereof
WO2022057666A1 (en) Positive electrode sheet and battery
CN111180644A (en) Lithium ion battery diaphragm with ultrathin coating layer
CN106450115A (en) Inorganic coated bacterial cellulose porous thin film and preparation method thereof
CN114057488B (en) Preparation method of porous SiOC ceramic and application of porous SiOC ceramic in negative electrode material of lithium ion battery
CN115395091A (en) High-performance composite solid electrolyte membrane and preparation method and application thereof
CN113937419B (en) Ceramic diaphragm based on organic-inorganic composite binder and preparation method thereof
CN114374055B (en) High-mechanical-strength, high-flame-retardance and high-adhesion battery diaphragm and preparation method thereof
CN111403661A (en) Composite diaphragm for power lithium ion battery and preparation method thereof
CN113235300B (en) Preparation method of high-temperature-resistant lithium ion battery composite diaphragm
CN113178562B (en) Fabric-like carbon-coated silicon dioxide composite material and application thereof
CN111477819B (en) Full-ceramic diaphragm for lithium ion battery and preparation method thereof
CN115172865B (en) Composite solid electrolyte membrane and preparation method and application thereof
CN110911619A (en) Lithium battery diaphragm, preparation method thereof and lithium battery
CN111244361A (en) Modified polyolefin diaphragm and preparation method and application thereof
CN114421091A (en) Preparation method of lithium battery composite diaphragm with multilayer structure
CN114243209A (en) Composite diaphragm material and preparation method and application thereof
CN115548575B (en) Baking-free all-inorganic lithium ion battery diaphragm and preparation method thereof
CN112928243B (en) Self-supporting nickel sulfide electrode and preparation and application thereof
CN116365167A (en) Battery diaphragm and preparation method and application thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant