CN116666635A - Preparation method of lithium-sulfur battery based on high-performance water-based binder - Google Patents

Preparation method of lithium-sulfur battery based on high-performance water-based binder Download PDF

Info

Publication number
CN116666635A
CN116666635A CN202310660526.1A CN202310660526A CN116666635A CN 116666635 A CN116666635 A CN 116666635A CN 202310660526 A CN202310660526 A CN 202310660526A CN 116666635 A CN116666635 A CN 116666635A
Authority
CN
China
Prior art keywords
lithium
sulfur
battery
carbon
binder
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.)
Pending
Application number
CN202310660526.1A
Other languages
Chinese (zh)
Inventor
张昊男
许侃
张子天
王皓月
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.)
Dalian University of Technology
Original Assignee
Dalian University of Technology
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 Dalian University of Technology filed Critical Dalian University of Technology
Priority to CN202310660526.1A priority Critical patent/CN116666635A/en
Publication of CN116666635A publication Critical patent/CN116666635A/en
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
    • C08H6/00—Macromolecular compounds derived from lignin, e.g. tannins, humic acids
    • 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
    • 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
    • H01M10/058—Construction or manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0404—Methods of deposition of the material by coating on electrode collectors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • 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)
  • Materials Engineering (AREA)
  • Biochemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention belongs to the technical field of lithium-sulfur battery binder materials, and discloses a preparation method of a lithium-sulfur battery based on a high-performance water-based binder. According to the invention, sodium lignin sulfonate and lithium lignin sulfonate are used as binders of lithium-sulfur batteries. The aqueous binder added in the lithium-sulfur battery is more friendly to the environment and can make the uterine power supply more stable so as to cope with stricter environmental protection policy. Besides, the high-nickel positive electrode material and the silicon-carbon negative electrode material can be adopted to further improve the energy density of the lithium ion battery.

Description

Preparation method of lithium-sulfur battery based on high-performance water-based binder
Technical Field
The invention belongs to the technical field of lithium-sulfur battery binder materials, and relates to a method for preparing a lithium-sulfur battery by using a high-performance water-based binder.
Background
Classes of existing batteries for energy storage problems include:
1. oil-based adhesive
For example: a fluoropolymer binder.
Fluoropolymers, such as Polytetrafluoroethylene (PTFE) and polyvinylidene fluoride (PVDF), find wide application in the field of lithium sulfur battery binders. Yamin et al (H.Yamin, E.Peled.Electrochemistry of a nonaqueous lithium/sulfur cell [ J ], power Sources 1983,9,281-287.) originally used PTFE as a binder for high specific surface area carbon composite electrodes, but these original studies utilized lithium polysulfide as the active material for the electrode (rather than sulfur). For a long time thereafter, PVDF was the predominant binder in lithium sulfur batteries. But PVDF has toxicity, undesirable mechanical properties and weak adsorption capacity for lithium polysulfide, so that researchers have to find its alternatives.
For example: polar/ionic polymer binders.
Polar/ionic polymers can mitigate diffusion of lithium polysulfide by dipole interactions. Schneider et al (Schneider, H.Garsuch, A.Panchenko, et al Influence of different electrode compositions and binder materials on the performance of lithium-sulfour bacteria [ J ]]Power Sources 2012,205,420-425.) has proven Nafion to be a viable binder material, but even with the application of an additional Nafion layer applied to the sulfur electrode, there is still a significant amount of lithium polysulfide dissolved. Li et al (G.Li, W.Cai, B.Liu, et al, amuli functional binder with lithium ion conductive polymer and polysulfide absorbents to improve cycleability of lithium-sulphur bacteria [ J]Power Sources 2015,294,187-192.) found in lithiated Nafion (Li) + Nafion) works better as a binder. Research shows that Li + Nafion and PVP are more effective as multicomponent mixed binders than alone, and the incorporation of silica (SiO 2) further improves cell performance, with reversible capacities exceeding 1100mAh g after 50 cycles -1 。
Such methods have limitations in that:
a. the adhesive has single performance, and cannot inhibit the shuttle effect of the polysulfide;
b. the high-temperature electrochemical stability is poor, and the electrolyte is easy to swell:
c. the cost is high, and the pollution is high;
d. the conductivity is poor.
2. Synthetic aqueous binder
For example: polyacrylic acid (PAA) binders and polyvinyl alcohol (PVA) binders.
Zhang et al (Z.Zhang, W.Bao, H.Lu, M.Jia, K.Xie, Y.Lai, J.Li, ECS electrochem. Lett.2012,1, a 34.) used PAA as a lithium sulfur battery binder. Experimental results show that the current density is 335mAg-1, the current is circulated for 500 times, the discharge capacity of the lithium sulfur battery using PAA as the binder is 325mAh g-1, and the coulomb efficiency is 89.5%. However, under the same condition, the discharge capacity of the lithium sulfur battery taking PVDF as a binder is only 204mAh g-1, and the coulombic efficiency is 83.6%. In addition, electrochemical tests have shown that lithium sulfur batteries with PAA as a binder have better kinetics, lower resistance, and longer cycling stability than lithium sulfur batteries with PVDF as a binder. Comparing the morphology of the sulfur electrode before and after 50 times of circulation by using a Scanning Electron Microscope (SEM) to a lithium sulfur battery using PAA as a binder, the morphology of the sulfur electrode is observed to be porous before circulation, lithium polysulfide can be adsorbed, and lithium ions (Li + ) Is transported by the transport system. But after cycling due to Li 2 S and Li 2 S 2 A solid film was formed on the surface of the sulfur electrode, the original porous morphology became dense, and cracks were observed.
For example: a polyacrylic emulsion binder.
LA132 is a water-soluble copolymer having a strong tackiness due to its cyano group (-CN). Pan et al (Jin Pan, guiyin Xu, bing Ding, et al enhanced electrochemical performance of sulfur cathodes with a water-soluble binder [ J)]RSC adv.2015,5,13709) found that the sulfur/LA 132-5wt% electrode had higher battery capacity and cycling stability than the S/PVDF-10wt electrode. Scanning Electron Microscope (SEM) observation shows that 5% of LA132 in the sulfur electrode can inhibit Li 2 S 2 And Li (lithium) 2 S is formed, and the porous structure of the sulfur electrode is maintained. However, the LA132 binder should not be used in excessive amounts, otherwise Li is caused 2 S 2 And Li (lithium) 2 S irreversibly bonds during cycling, reducing the potential between the electrode and electrolyteAnd (3) contact. In addition, the experimental result shows that the lithium sulfur battery using LA132 as the binder has smaller internal resistance and better dynamic performance than the lithium sulfur battery using PVDF as the binder.
Such methods have limitations in that:
a. the synthetic water-based binder is a high-molecular polymer, and the processing technology is complex.
b. The partially synthetic aqueous binder is environmentally friendly.
c. High cost and difficult commercialization.
In view of the problems in the prior art, the present invention provides a method for preparing a high-performance aqueous binder for lithium-sulfur batteries.
Disclosure of Invention
The invention combines two types of lignosulfonates: sodium lignin sulfonate (LSNa) and lithium Lignin Sulfonate (LSLi) are used as binders for lithium sulfur batteries. On one hand, the shuttle effect of the lithium-sulfur battery can be effectively inhibited, and the shuttle effect can be effectively inhibited due to polar groups such as lignosulfonate and the like, so that the transportation of lithium ions can be promoted, and the lithium polysulfide has a chemical adsorption effect; on the other hand, lignin has wide source, low price and environmental protection, is mainly from the pulping process of paper, is a main waste byproduct in the pulping industry, and has annual output of up to 7000 ten thousand tons.
The technical scheme of the invention is as follows:
a method for preparing a lithium-sulfur battery by using a high-performance water-based binder comprises the following steps:
(1) The Critical Aggregation Concentration (CAC) of sodium lignin sulfonate in an aqueous solution is 0.05g/L, and when the concentration is lower than the CAC, a large amount of single molecules and a small amount of aggregates exist in the solution; when the concentration is higher than CAC, the number of single molecules decreases, while the number of aggregates increases rapidly. Preparing a sodium lignin sulfonate aqueous solution with the concentration of 0.05g/L, adding cation exchange resin into the sodium lignin sulfonate aqueous solution, heating and stirring for 48 hours at 35 ℃ to ensure that ions are fully exchanged; filtering out cation exchange resin to obtain aqueous solution (LS) of lignin sulfonic acid, and drying in a blast oven to obtain lignin sulfonic acid powder;
(2) Dissolving lignin sulfonic acid and lithium hydroxide with equal molar mass in deionized water, and heating and stirring at 60 ℃ for reaction for 72 hours to obtain lithium lignin sulfonate LSLi;
(3) According to the mass ratio of 8:1:1, uniformly mixing S/KJC, LSLi and conductive agent acetylene black in deionized water, uniformly coating the obtained slurry on a carbon-coated aluminum foil, drying in a vacuum oven at 60 ℃ for 24 hours, and performing piece cutting treatment after the pole piece is completely cooled and dried to obtain a round lithium-sulfur battery positive electrode piece with the diameter of 14 mm;
(4) The battery shell used for assembling the lithium-sulfur battery is of a button CR2032 type, and the whole assembling process is carried out in a glove box; and (3) taking a lithium sheet as a battery cathode, single-layer polypropylene as a diaphragm and an ether solvent as an electrolyte, and obtaining the battery anode in the step (3).
Further, the preparation method of the sulfur-carbon composite material (S/KJC) comprises the following steps: sublimed sulfur with ketjen black carbon (KJC) at 2:1, grinding uniformly in a mass ratio to prepare a sulfur-carbon mixture; the sulfur-carbon mixture was heated in a vacuum oven at 155 c for 16 hours to allow sulfur to infiltrate into the pores of the carbon material, resulting in a sulfur-carbon composite (S/KJC).
Further, 2wt% LiNO was added to a 1M solution of lithium bistrifluoromethanesulfonimide as an electrolyte 3 The lithium bis (trifluoromethanesulfonyl) imide solution is prepared by dissolving bis (trifluoromethanesulfonyl) imide lithium solution in 1:1 dioxolane and ethylene glycol dimethyl ether.
Further, the size diameter of the negative electrode used in the battery is 15.5mm, the size diameter of the polypropylene separator is 19mm, and the surface loading of sulfur in the positive electrode of each round battery is kept between 1.0 and 1.5mg/cm 2 The amount of electrolyte added and the lithium storage active material (lithium cobalt oxide LiCoO) 2 ) The ratio was controlled at 20. Mu.L/mg.
The invention has the beneficial effects that:
with the increasing environmental protection and battery energy density requirements, the development of aqueous adhesives is more environmentally friendly and can make uterine power more stable to cope with stricter environmental policies. Besides, the high-nickel positive electrode material and the silicon-carbon negative electrode material can be adopted to further improve the energy density of the lithium ion battery.
Besides this, the following advantages are achieved: (1) The adhesive property is good, the tensile strength is high, the flexibility is good, and the Young's modulus is low; (2) The chemical stability and the electrochemical stability are good, and the reaction and the deterioration are avoided in the storage and the circulation process; (3) no swelling or a small swelling coefficient in the electrolyte; (3) The dispersion in the slurry medium is good, which is favorable for uniformly bonding the active substances on the current collector; (4) The influence on the conduction of electrons and ions in the electrode is small; and (5) the method is environment-friendly, safe to use and low in cost.
Detailed Description
The following describes the embodiments of the present invention in further detail with reference to the drawings.
Example 1
A method for preparing a lithium-sulfur battery by using a high-performance water-based binder comprises the following steps:
(1) 1g of LSNa is dissolved in deionized water, cation exchange resin is added, heating and stirring are carried out for 48 hours at 35 ℃ to ensure that ions are fully exchanged, the cation exchange resin is filtered to obtain aqueous solution (LS) of lignin sulfonic acid, and lignin sulfonic acid powder is obtained after drying in a blast oven for subsequent testing.
(2) Dissolving lignin sulfonic acid and lithium hydroxide with equal molar mass in deionized water, heating and stirring for 72 hours at 60 ℃ to enable the lignin sulfonic acid and the lithium hydroxide to fully react to generate LSLi;
the synthetic route is as follows:
(3) Uniformly mixing S/KJC (the sublimed sulfur and the Ketjen black carbon (KJC) are uniformly ground in a mass ratio of 2:1 to prepare a sulfur-carbon mixture, heating the sulfur-carbon mixture in a vacuum box at 155 ℃ for 16 hours, enabling sulfur to permeate into pores of a carbon material, marking the obtained sulfur-carbon composite material as (S/KJC)), LSLi and a commercial conductive agent acetylene black in a small amount of deionized water, uniformly coating the obtained slurry on a carbon-coated aluminum foil, drying in a vacuum oven at 60 ℃ for 24 hours, and performing cutting treatment after the pole piece is completely cooled and dried to obtain a circular lithium-sulfur battery positive electrode piece with the diameter of 14 mm;
(4) The battery shell used for assembling the lithium-sulfur battery is button CR2032 type, and the whole assembling process is carried out in a glove box. Lithium sheets are used as a battery cathode, monolayer polypropylene (PP, celgard 2500) is used as a diaphragm, an ether-based solvent is used as an electrolyte, and the prepared carbon-sulfur compound is used as a battery anode to assemble a button battery and is subjected to electrochemical test.
Comparative example 1
A method for preparing a lithium-sulfur battery by using a high-performance water-based binder comprises the following steps:
(1) 1g of LSNa is dissolved in deionized water, cation exchange resin is added, heating and stirring are carried out for 48 hours at 35 ℃ to ensure that ions are fully exchanged, the cation exchange resin is filtered to obtain aqueous solution (LS) of lignin sulfonic acid, and lignin sulfonic acid powder is obtained after drying in a blast oven for subsequent testing.
(2) Dissolving lignin sulfonic acid and lithium hydroxide with equal molar mass in deionized water, heating and stirring for 72 hours at 60 ℃ to enable the lignin sulfonic acid and the lithium hydroxide to fully react to generate LSLi;
(3) S/KJC (90% wt%) was employed separately mixed with binder (10% wt%) and the positive electrode was free of additional conductive agent. The resulting slurries were coated on carbon-coated aluminum foils, respectively, and dried under vacuum at 60 ℃ for 12 hours. Cutting the dried pole piece into a circular positive pole piece with the diameter of 14mm by using a slicer.
(4) The battery shell used for assembling the lithium-sulfur battery is button CR2032 type, and the whole assembling process is carried out in a glove box. Lithium sheets are used as a battery cathode, monolayer polypropylene (PP, celgard 2500) is used as a diaphragm, an ether-based solvent is used as an electrolyte, and the prepared carbon-sulfur compound is used as a battery anode to assemble a button battery and is subjected to electrochemical test.
Supplementary results analysis:
(1) Lithium sulfur battery performance: in example 1, a mixture of S/KJC with LSLi and acetylene black was used as a positive electrode material, and in comparative example 1, a mixture of S/KJC with a binder was used as a positive electrode material. Because acetylene black is a commercial conductive agent and has better conductive performance, the positive electrode material of example 1 may have better conductive performance, so that the electrochemical performance and the cycling stability of the lithium-sulfur battery are expected to be improved.
(2) Energy density: a high performance aqueous binder was used in example 1, which may help to increase the energy density of the battery. In contrast, the use of the binder mixture in comparative example 1 may have some effect on the energy density of the battery. Thus, it is expected that example 1 may have a higher energy density.
(3) Interfacial stability: since a high-performance aqueous binder is used in example 1, this may contribute to an improvement in interface stability between the positive electrode material and the electrolyte. This can reduce interfacial reaction and loss of electrolyte during cycling of the battery, thereby improving cycle life and capacity retention of the battery.

Claims (4)

1. The preparation method of the lithium sulfur battery based on the high-performance water-based binder is characterized by comprising the following steps:
(1) Preparing a sodium lignin sulfonate aqueous solution with the concentration of 0.05g/L, adding cation exchange resin into the sodium lignin sulfonate aqueous solution, heating and stirring for 48 hours at 35 ℃ to ensure that ions are fully exchanged; filtering out cation exchange resin to obtain aqueous solution of lignin sulfonic acid, and drying in a blast oven to obtain lignin sulfonic acid powder;
(2) Dissolving lignin sulfonic acid and lithium hydroxide with equal molar mass in deionized water, and heating and stirring at 60 ℃ for reaction for 72 hours to obtain lithium lignin sulfonate LSLi;
(3) According to the mass ratio of 8:1: uniformly mixing a sulfur-carbon composite material S/KJC, LSLi and an electric conduction agent acetylene black in deionized water, uniformly coating the obtained slurry on a carbon-coated aluminum foil, drying in a vacuum oven at 60 ℃ for 24 hours, and performing cutting treatment after the pole piece is completely cooled and dried to obtain a round lithium-sulfur battery positive electrode piece with the diameter of 14 mm;
(4) The battery shell used for assembling the lithium-sulfur battery is of a button CR2032 type, and the whole assembling process is carried out in a glove box; and (3) taking a lithium sheet as a battery cathode, single-layer polypropylene as a diaphragm and an ether solvent as an electrolyte, and obtaining the battery anode in the step (3).
2. The method according to claim 1, wherein the preparation method of the sulfur-carbon composite material S/KJC is as follows: sublimed sulfur and ketjen black carbon KJC at 2:1, grinding uniformly in a mass ratio to prepare a sulfur-carbon mixture; and heating the sulfur-carbon mixture in a vacuum box at 155 ℃ for 16 hours to enable sulfur to permeate into pores of the carbon material, so as to obtain the sulfur-carbon composite material S/KJC.
3. The method according to claim 1, wherein 2wt% LiNO is added to 1M lithium bistrifluoro-methanesulfonimide solution as electrolyte 3 The lithium bis (trifluoromethanesulfonyl) imide solution is prepared by dissolving bis (trifluoromethanesulfonyl) imide lithium solution in 1:1 dioxolane and ethylene glycol dimethyl ether.
4. A method according to claim 3, wherein the size diameter of the negative electrode used in the cell is 15.5mm, the size diameter of the polypropylene separator is 19mm, and the surface loading of sulfur in the positive electrode of each circular cell is maintained at 1.0-1.5 mg/cm 2 Electrolyte and lithium cobalt oxide LiCoO 2 The mass ratio of (C) was controlled at 20. Mu.L/mg.
CN202310660526.1A 2023-06-06 2023-06-06 Preparation method of lithium-sulfur battery based on high-performance water-based binder Pending CN116666635A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202310660526.1A CN116666635A (en) 2023-06-06 2023-06-06 Preparation method of lithium-sulfur battery based on high-performance water-based binder

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202310660526.1A CN116666635A (en) 2023-06-06 2023-06-06 Preparation method of lithium-sulfur battery based on high-performance water-based binder

Publications (1)

Publication Number Publication Date
CN116666635A true CN116666635A (en) 2023-08-29

Family

ID=87718677

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202310660526.1A Pending CN116666635A (en) 2023-06-06 2023-06-06 Preparation method of lithium-sulfur battery based on high-performance water-based binder

Country Status (1)

Country Link
CN (1) CN116666635A (en)

Similar Documents

Publication Publication Date Title
CN109167012B (en) Multilayer composite structure diaphragm, preparation method thereof and lithium-sulfur battery
CN109004220B (en) Boric acid compound modified lithium ion battery silicon cathode and preparation method thereof
Sun et al. Effect of poly (acrylic acid)/poly (vinyl alcohol) blending binder on electrochemical performance for lithium iron phosphate cathodes
CN108682820B (en) Silicon-carbon composite negative electrode material, negative electrode plate, preparation method of negative electrode plate and lithium ion battery
CN111600020B (en) Lithium ion battery and preparation method thereof
CN111430716B (en) Water-based soy protein-based supermolecule sulfur positive electrode binder and preparation method and application thereof
Cheng et al. Oxidized multiwall carbon nanotube modified separator for high performance lithium–sulfur batteries with high sulfur loading
CN102437369B (en) Lithium ion battery
CN111540868A (en) Preparation method and application of two-dimensional manganese dioxide modified polypropylene diaphragm
CN113651935B (en) Porous polymer-sulfur composite material and preparation method and application thereof
CN113555541A (en) High-energy-density lithium ion battery
JP5632246B2 (en) Lithium ion secondary battery
Xiong et al. SiO x-based graphite composite anode and efficient binders: practical applications in lithium-ion batteries
CN110993952A (en) Preparation method of positive and negative electrode conductive liquid storage layer slurry and thick electrode
KR101657742B1 (en) Positive electrode for secondary battery and the method for manufacturing the same
CN113193196A (en) Multifunctional aqueous binder for sodium ion battery and application thereof
CN113285050A (en) Li-M-X-based solid lithium battery anode and preparation method thereof
CN116364930A (en) Compound additive and electrochemical device using same
CN113363482B (en) Composite binder for silicon-based negative electrode of lithium ion battery and preparation method and application thereof
CN115159527A (en) Hard carbon coated silicon nanoparticle composite microsphere negative electrode material and preparation method and application thereof
CN116666635A (en) Preparation method of lithium-sulfur battery based on high-performance water-based binder
CN114583094A (en) Lithium ion battery capable of improving low-temperature performance and preparation method thereof
CN115347149A (en) Ultra-dispersed nano composite conductive adhesive and preparation method and application thereof
CN112382763A (en) Organic matter/silicon composite material, battery cathode obtained from organic matter/silicon composite material and preparation method of battery cathode
CN112271324A (en) High-voltage solid-state lithium battery and preparation method 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