CN109301218A - A kind of preparation method of lithium manganate battery cathode - Google Patents
A kind of preparation method of lithium manganate battery cathode Download PDFInfo
- Publication number
- CN109301218A CN109301218A CN201811172095.XA CN201811172095A CN109301218A CN 109301218 A CN109301218 A CN 109301218A CN 201811172095 A CN201811172095 A CN 201811172095A CN 109301218 A CN109301218 A CN 109301218A
- Authority
- CN
- China
- Prior art keywords
- parts
- negative electrode
- preparation
- lithium manganate
- battery cathode
- 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
Links
Classifications
-
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
-
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
-
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
-
- 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)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Composite Materials (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention proposes a kind of preparation methods of lithium manganate battery cathode, the negative electrode material is coated uniformly on negative electrode slurry on Si-As-Se/C composite Nano negative electrode material copper foil, after 80 DEG C of dry 10-12h solidifications, rolled using roller to 30-70 μm, then obtained with sheet-punching machine punching；The negative electrode slurry is made by N-methyl pyrrolidones, Si-As-Se/C composite Nano negative electrode material, binder, thickener, conductive agent, film forming agent, pore creating material, antioxidant.Raw material sources of the present invention are wide, and preparation method is simple, and negative electrode material electrochemical performance obtained can be widely used in modern market field of lithium.
Description
Technical field
The present invention relates to technical field of lithium ion, and in particular to a kind of lithium manganate battery cathode.
Background technique
Lithium battery is the secondary cell of new generation developed rapidly the 1990s, is widely used in small portable electricity
Sub- communication product and electric vehicle.Traditional nickel-metal hydride battery, nickel-cadmium cell, lead-acid battery are sold supporting shadow by lithium battery
It rings, mobile phone and laptop lithium battery high-end market are tied up, and lithium battery demand is accordingly significantly increased.
Spinel type lithium titanate (Li4Ti5O12) have the characteristics that not available for carbon material: belong to zero strain material, charge and discharge
Skeleton in electric process remains unchanged；Charge and discharge platform height [1.5V (vs.Li/Li+)], the deposition of lithium metal will not occur；Tool
There is Li+Three-dimensional diffusion channel, Li+ diffusion coefficient 1 order of magnitude higher than carbon negative pole material.With Li4Ti5O12Replace carbon material conduct
Cathode can improve safety and the power-performance of lithium ion battery, extend cycle life.With cobalt acid lithium (LiCoO2) compare, point
Spar type LiMn2O4 (LiMn2O4) there is low abundant raw material, price, non-environmental-pollution, easily recycling, current potential are high and safety is good etc.
Advantage.
The superiority and inferiority and composition of negative electrode slurry are an important factor for significantly affecting performance of lithium ion battery and cycle life, even
As its restraining factors.Current lithium ion battery anode slurry can be divided into oil slurry and aqueous slurry, and differentiation foundation is
The polarity of solvent.It is solvent that oil slurry uses N-methyl pyrrolidones more, and Kynoar is binder.Aqueous slurry then with
Water is solvent, and sodium carboxymethylcellulose is thickener, and SBR emulsion is binder.Cost is relatively low with it for aqueous slurry, ring
Border pressure is small and has obtained the generally use of factory.It is by active material, thickener, conduction that conventional method, which prepares negative electrode slurry,
Agent, binder successively add and stir and be made, however this mode be unfavorable for stirring evenly and whole preparation process time-consuming compared with
It is long.In addition, also often occurring in the actual production process since negative electrode slurry stability is poor, so that storage generation for a long time is heavy
The phenomenon that drop, agglomeration, post-production performance is poor, affects electric conductivity and working efficiency.On cathode composition, in addition to cathode
Outside slurry, electrolyte and film forming agent are also vital component part, are related to the change of solid electrolyte interface (SEI) film
Composition, Structure and stability etc. are learned, is the key that determine lithium ion batteries anodes and compatibility of electrolyte.In addition, pore creating material
Also will affect the porosity of negative electrode tab, even pore distribution is conducive to the conduction for improving lithium ion, make obtained lithium from
The high rate performance of sub- battery is improved with high temperature cyclic performance.In current production application, especially improvement battery is interior
Resistance, promotes the high rate performance and high circulation performance of battery, selects the adding technology and composition of highly efficient film forming agent, pore creating material,
It is the important factor in order of lithium ion battery quality.
Therefore, the more effective and stable negative electrode slurry composition of one kind and preparation method are explored, point of negative electrode slurry is improved
Effect is dissipated, the internal resistance of battery is reduced, promotes cycle life under the high rate performance and high power of battery, to improve the various of battery
Chemical property undoubtedly has great importance.
Summary of the invention
In order to solve the above technical problems, the present invention provides a kind of preparation method of lithium manganate battery cathode, purpose
It is, by preparing Si-As-Se/C composite Nano negative electrode material, and coats high-effect negative electrode slurry, the negative electrode slurry is with reasonable
Ratio adds binder, conductive agent and other compositions etc., so that battery has preferable chemical property, cycle-index exists
At 1000 times, the capacity retention ratio of battery is 90% or more；Cathode is in 0.5C multiplying power discharging, obtained battery specific capacity 550-
620mAh/g, in 10C multiplying power discharging, specific capacity 510-530mAh/g, in 15C multiplying power discharging, specific capacity 480-
500mAh/g。
The present invention provides a kind of preparation method of lithium manganate battery cathode, and the negative electrode material is uniformly to apply negative electrode slurry
It overlays on Si-As-Se/C composite Nano negative electrode material copper foil, after 80 DEG C of dry 10-12h solidifications, is rolled using roller to 30-
70 μm, then obtained with sheet-punching machine punching；The negative electrode slurry is by N-methyl pyrrolidones, Si-As-Se/C composite Nano cathode material
Material, binder, thickener, conductive agent, film forming agent, pore creating material, antioxidant are made, 100-120 parts of the N-methyl pyrrolidones,
It is 80-100 parts of the Si-As-Se/C composite Nano negative electrode material, binder 5-10 parts described, thickener 5-15 parts described, described
It is 10-20 parts of conductive agent, film forming agent 5-20 parts described, pore creating material 1-10 parts described, antioxidant 5-15 parts described；
The Si-As-Se/C composite Nano negative electrode material the preparation method is as follows:
(1) it weighs suitable polyacrylonitrile to be dissolved in DMSO solution, stirs to being completely dissolved, be configured to poly- the third of 10%
Alkene nitrile/DMSO solution is added nano silica fume and continues to stir evenly；
(2) weigh acetic acid arsenic, acetic acid selenide is dissolved in DMSO, stirring is to being completely dissolved；
(3) two kinds of solution obtained in step (1) and step (2) are mixed, high-voltage electrostatic spinning, obtains after mixing evenly
Non-woven membrane, as 2-5h is pre-oxidized in air, in 270 DEG C of heating rate low-temperature bake 5h with 5 DEG C/min, in Ar gas bar part
Under as 400-600 DEG C of high-temperature calcination 3-6h of Muffle furnace, after carbonization be made；
The ratio between amount of substance of the acetic acid arsenic, acetic acid selenide and nano silica fume is 3:2:10；
The negative electrode slurry the preparation method is as follows: by Si-As-Se/C composite Nano negative electrode material, binder, thickening
Agent, conductive agent, antioxidant are dissolved in N-methyl pyrrolidones, and ultrasonic mixing dissolution stirs evenly, pore creating material is added, is warming up to
70 DEG C, stirring and dissolving is added film forming agent, rises to 85 DEG C, stir evenly, be cooled to room temperature, obtain gluey slurries, is made,.
As further improvement of the invention, high-voltage electrostatic spinning step condition is voltage 15KV, and temperature is 30-40 DEG C,
Drum rotation speed is 50r/min, and solidification distance is 10-12cm.
As further improvement of the invention, negative electrode slurry is prepared by following raw material: N-methyl pyrrolidines
105-112 parts of ketone, 85-93 parts of Si-As-Se/C composite Nano negative electrode material, 7-9 parts of binder, 7-12 parts of thickener, conductive agent
12-17 parts, 9-15 parts of film forming agent, 3-7 parts of pore creating material, 8-13 parts of antioxidant.
As further improvement of the invention, negative electrode slurry is prepared by following raw material: N-methyl pyrrolidines
110 parts of ketone, 89 parts of Si-As-Se/C composite Nano negative electrode material, 8 parts of binder, 9 parts of thickener, 15 parts of conductive agent, film forming agent
13 parts, 6 parts of pore creating material, 12 parts of antioxidant.
As further improvement of the invention, binder is selected from polyvinyl alcohol, LA132, polytetrafluoroethylene (PTFE), polyurethane, carboxylic
One of sodium carboxymethylcellulose pyce or Viton.
As further improvement of the invention, thickener is selected from methylcellulose, carboxymethyl cellulose, hydroxy ethyl fiber
Element, hydroxypropyl methyl cellulose, acrylic acid, methacrylic acid, polyacrylamide, polyvinyl alcohol, polyvinylpyrrolidone, polyoxy
Change ethylene, carbomer, polyacrylic acid, Sodium Polyacrylate, butadiene rubber, butadiene-styrene rubber, polyurethane, modified polyurea or low molecule
One or more of polyethylene wax.
Improved as of the invention further, conductive agent be selected from acetylene black, Super P, Super S, 350G, carbon fiber,
One or more of carbon nanotube or Ketjen black.
As further improvement of the invention, film forming agent is cellulose nitrate film forming agent.
As further improvement of the invention, pore creating material is selected from PS microballoon, PMMA microsphere, ceramic microbead, coal dust or carbon black
One of.
As further improvement of the invention, antioxidant is selected from diphenylamines, p-phenylenediamine, dihydroquinoline, 2,6- three-level fourth
Base -4- methylphenol, bis- (3,5- three-level butyl -4- hydroxy phenyl) thioethers or four (β-(3,5- three-level butyl -4- hydroxy phenyl)
One or more of propionic acid) pentaerythritol ester.
The invention has the following beneficial effects:
1. the present invention coats high-effect negative electrode slurry by preparation Si-As-Se/C composite Nano negative electrode material, this is negative
Pole slurry is with rational proportion addition binder, conductive agent and other compositions etc., so that battery has preferable chemical property,
For cycle-index at 1000 times, the capacity retention ratio of battery is 90% or more；Cathode is in 0.5C multiplying power discharging, obtained battery
Specific capacity 550-620mAh/g, in 10C multiplying power discharging, specific capacity 510-530mAh/g, in 15C multiplying power discharging, specific volume
Amount is 480-500mAh/g；
2. raw material sources of the present invention are wide, preparation method is simple, and negative electrode material electrochemical performance obtained can answer extensively
In modern market field of lithium.
Detailed description of the invention
Fig. 1 is the preparation technology figure of lithium manganate battery cathode.
Specific embodiment
Below in conjunction with the embodiment of the present invention, the technical scheme in the embodiment of the invention is clearly and completely described,
Obviously, the embodiment described is the embodiment of part of representative of the invention, rather than whole embodiments, this field are general
Other all embodiments obtained belong to protection of the invention to logical technical staff without making creative work
Range.
The preparation of 1 lithium manganate battery cathode of embodiment
One, the preparation of negative electrode slurry:
100 parts of N-methyl pyrrolidones, 80 parts of Si-As-Se/C composite Nano negative electrode material, 5 parts of Viton, carboxymethyl
5 parts of cellulose, 10 parts of Ketjen black, 5 parts of cellulose nitrate film forming agent, 1 part of carbon black, 5 parts of diphenylamines；
The preparation method is as follows: by Si-As-Se/C composite Nano negative electrode material, Viton, carboxymethyl cellulose, section's qin
Black, diphenylamines is dissolved in N-methyl pyrrolidones, and ultrasonic mixing dissolution stirs evenly, carbon black is added, and is warming up to 70 DEG C, stirring
Dissolution is added cellulose nitrate film forming agent, rises to 85 DEG C, stir evenly, be cooled to room temperature, obtain gluey slurries, is made.
Two, the preparation of Si-As-Se/C composite Nano negative electrode material:
(1) it weighs suitable polyacrylonitrile to be dissolved in DMSO solution, stirs to being completely dissolved, be configured to poly- the third of 10%
Alkene nitrile/DMSO solution is added 10mol nano silica fume and continues to stir evenly；
(2) weigh 3mol acetic acid arsenic, 2mol acetic acid selenide is dissolved in DMSO, stirring is to being completely dissolved；
(3) two kinds of solution obtained in step (1) and step (2) are mixed, after mixing evenly high-voltage electrostatic spinning, high pressure
Electrostatic spinning step condition is voltage 15KV, and temperature is 30 DEG C, drum rotation speed 50r/min, and solidification distance is 10cm, obtains nothing
Woven fabric film, as pre-oxidizing 2h in air, in 270 DEG C of heating rate low-temperature bake 5h with 5 DEG C/min, Ar gas bar part down toward
In 400 DEG C of high-temperature calcination 3h of Muffle furnace, it is made after carbonization.
Three, the preparation of lithium manganate battery cathode:
Negative electrode material is coated uniformly on negative electrode slurry on Si-As-Se/C composite Nano negative electrode material copper foil, and 80 DEG C dry
After dry 10h solidification, rolled using roller to 30 μm, then obtained with sheet-punching machine punching.
The preparation of 2 lithium manganate battery cathode of embodiment
One, the preparation of negative electrode slurry:
120 parts of N-methyl pyrrolidones, 100 parts of Si-As-Se/C composite Nano negative electrode material, 10 parts of polyurethane, polypropylene
15 parts of amide, 20 parts of carbon nanotube, 20 parts of cellulose nitrate film forming agent, 10 parts of coal dust, four (β-(3,5- three-level butyl -4- hydroxy benzenes
Base) propionic acid) 15 parts of pentaerythritol ester；
The preparation method is as follows: by Si-As-Se/C composite Nano negative electrode material, polyurethane, polyacrylamide, carbon nanotube,
Four (β-(3,5- three-level butyl -4- hydroxy phenyl) propionic acid) pentaerythritol esters are dissolved in N-methyl pyrrolidones, and ultrasonic mixing is molten
Solution, stirs evenly, and coal dust is added, and is warming up to 70 DEG C, and cellulose nitrate film forming agent is added in stirring and dissolving, rises to 85 DEG C, stirring is equal
It is even, it is cooled to room temperature, obtains gluey slurries, is made.
Two, the preparation of Si-As-Se/C composite Nano negative electrode material:
(1) it weighs suitable polyacrylonitrile to be dissolved in DMSO solution, stirs to being completely dissolved, be configured to poly- the third of 10%
Alkene nitrile/DMSO solution is added 10mol nano silica fume and continues to stir evenly；
(2) weigh 3mol acetic acid arsenic, 2mol acetic acid selenide is dissolved in DMSO, stirring is to being completely dissolved；
(3) two kinds of solution obtained in step (1) and step (2) are mixed, after mixing evenly high-voltage electrostatic spinning, high pressure
Electrostatic spinning step condition is voltage 15KV, and temperature is 40 DEG C, drum rotation speed 50r/min, and solidification distance is 10-12cm, is obtained
To non-woven membrane, as 5h is pre-oxidized in air, in 270 DEG C of heating rate low-temperature bake 5h with 5 DEG C/min, in Ar gas bar part
Under as 600 DEG C of high-temperature calcination 6h of Muffle furnace, after carbonization be made.
Three, the preparation of lithium manganate battery cathode:
Negative electrode material is coated uniformly on negative electrode slurry on Si-As-Se/C composite Nano negative electrode material copper foil, and 80 DEG C dry
After dry 12h solidification, rolled using roller to 70 μm, then obtained with sheet-punching machine punching.
The preparation of 3 lithium manganate battery cathode of embodiment
One, the preparation of negative electrode slurry:
105 parts of N-methyl pyrrolidones, 85 parts of Si-As-Se/C composite Nano negative electrode material, 7 parts of polytetrafluoroethylene (PTFE), suitable fourth
7 parts of rubber, 12 parts of carbon fiber, 9 parts of cellulose nitrate film forming agent, 3 parts of PMMA microsphere, 8 parts of methylphenol of 2,6- three-level butyl -4-；
The preparation method is as follows: by Si-As-Se/C composite Nano negative electrode material, polytetrafluoroethylene (PTFE), butadiene rubber, carbon fiber,
2,6- three-level butyl -4- methylphenols are dissolved in N-methyl pyrrolidones, and ultrasonic mixing dissolution stirs evenly, it is micro- that PMMA is added
Ball, is warming up to 70 DEG C, and stirring and dissolving is added cellulose nitrate film forming agent, rises to 85 DEG C, stir evenly, be cooled to room temperature, obtain glue
Slurries are made.
Two, the preparation of Si-As-Se/C composite Nano negative electrode material:
(1) it weighs suitable polyacrylonitrile to be dissolved in DMSO solution, stirs to being completely dissolved, be configured to poly- the third of 10%
Alkene nitrile/DMSO solution is added 10mol nano silica fume and continues to stir evenly；
(2) weigh 3mol acetic acid arsenic, 2mol acetic acid selenide is dissolved in DMSO, stirring is to being completely dissolved；
(3) two kinds of solution obtained in step (1) and step (2) are mixed, after mixing evenly high-voltage electrostatic spinning, high pressure
Electrostatic spinning step condition is voltage 15KV, and temperature is 35 DEG C, drum rotation speed 50r/min, and solidification distance is 11cm, obtains nothing
Woven fabric film, as pre-oxidizing 3h in air, in 270 DEG C of heating rate low-temperature bake 5h with 5 DEG C/min, Ar gas bar part down toward
In 500 DEG C of high-temperature calcination 5h of Muffle furnace, it is made after carbonization.
Three, the preparation of lithium manganate battery cathode:
Negative electrode material is coated uniformly on negative electrode slurry on Si-As-Se/C composite Nano negative electrode material copper foil, and 80 DEG C dry
After dry 11h solidification, rolled using roller to 50 μm, then obtained with sheet-punching machine punching.
The preparation of 4 lithium manganate battery cathode of embodiment
One, the preparation of negative electrode slurry:
112 parts of N-methyl pyrrolidones, 93 parts of Si-As-Se/C composite Nano negative electrode material, LA1329 parts, modified polyurea
12 parts, 17 parts of 350G, 15 parts of cellulose nitrate film forming agent, 7 parts of PS microballoon, 13 parts of dihydroquinoline；
The preparation method is as follows: by Si-As-Se/C composite Nano negative electrode material, LA132, modified polyurea, 350G, dihydro quinoline
Quinoline is dissolved in N-methyl pyrrolidones, and ultrasonic mixing dissolution stirs evenly, PS microballoon is added, is warming up to 70 DEG C, stirring and dissolving,
Cellulose nitrate film forming agent is added, rises to 85 DEG C, stirs evenly, be cooled to room temperature, obtain gluey slurries, is made.
Two, the preparation of Si-As-Se/C composite Nano negative electrode material:
(1) it weighs suitable polyacrylonitrile to be dissolved in DMSO solution, stirs to being completely dissolved, be configured to poly- the third of 10%
Alkene nitrile/DMSO solution is added 10mol nano silica fume and continues to stir evenly；
(2) weigh 3mol acetic acid arsenic, 2mol acetic acid selenide is dissolved in DMSO, stirring is to being completely dissolved；
(3) two kinds of solution obtained in step (1) and step (2) are mixed, after mixing evenly high-voltage electrostatic spinning, high pressure
Electrostatic spinning step condition is voltage 15KV, and temperature is 35 DEG C, drum rotation speed 50r/min, and solidification distance is 11cm, obtains nothing
Woven fabric film, as pre-oxidizing 4h in air, in 270 DEG C of heating rate low-temperature bake 5h with 5 DEG C/min, Ar gas bar part down toward
In 500 DEG C of high-temperature calcination 5h of Muffle furnace, it is made after carbonization.
Three, the preparation of lithium manganate battery cathode:
Negative electrode material is coated uniformly on negative electrode slurry on Si-As-Se/C composite Nano negative electrode material copper foil, and 80 DEG C dry
After dry 11h solidification, rolled using roller to 60 μm, then obtained with sheet-punching machine punching.
The preparation of 5 lithium manganate battery cathode of embodiment
One, the preparation of negative electrode slurry:
110 parts of N-methyl pyrrolidones, 89 parts of Si-As-Se/C composite Nano negative electrode material, 8 parts of polyvinyl alcohol, low molecule
9 parts of polyethylene wax, 15 parts of Super P, 13 parts of cellulose nitrate film forming agent, 6 parts of ceramic microbead, 12 parts of p-phenylenediamine；
The preparation method is as follows: by Si-As-Se/C composite Nano negative electrode material, polyvinyl alcohol, low-molecular polyethylene wax,
Super P, p-phenylenediamine are dissolved in N-methyl pyrrolidones, and ultrasonic mixing dissolution stirs evenly, and ceramic microbead, heating is added
To 70 DEG C, stirring and dissolving is added cellulose nitrate film forming agent, rises to 85 DEG C, stir evenly, be cooled to room temperature, obtain gluey slurries, makes
?.
Two, the preparation of Si-As-Se/C composite Nano negative electrode material:
(1) it weighs suitable polyacrylonitrile to be dissolved in DMSO solution, stirs to being completely dissolved, be configured to poly- the third of 10%
Alkene nitrile/DMSO solution is added 10mol nano silica fume and continues to stir evenly；
(2) weigh 3mol acetic acid arsenic, 2mol acetic acid selenide is dissolved in DMSO, stirring is to being completely dissolved；
(3) two kinds of solution obtained in step (1) and step (2) are mixed, after mixing evenly high-voltage electrostatic spinning, high pressure
Electrostatic spinning step condition is voltage 15KV, and temperature is 35 DEG C, drum rotation speed 50r/min, and solidification distance is 11cm, obtains nothing
Woven fabric film, as pre-oxidizing 3.5h in air, in 270 DEG C of heating rate low-temperature bake 5h with 5 DEG C/min, under the conditions of Ar gas
As for 500 DEG C of high-temperature calcination 4.5h of Muffle furnace, it is made after carbonization.
Three, the preparation of lithium manganate battery cathode:
Negative electrode material is coated uniformly on negative electrode slurry on Si-As-Se/C composite Nano negative electrode material copper foil, and 80 DEG C dry
After dry 11h solidification, rolled using roller to 55 μm, then obtained with sheet-punching machine punching.
Reference examples 1 according to patent ZL 201610975186.1 " a kind of preparation method of lithium manganate battery cathode " method
Preparation
Negative electrode slurry preparation: weigh 1 parts by weight (by deionized water be 100 parts by weight in terms of) sodium carboxymethylcellulose with account for
The 30wt% deionized water of deionized water total amount mixes, and stirs 180min at normal temperature with the mixing speed of 500rpm, obtains glue
Shape solution；By colloidal solution, weigh 65 parts by weight (by deionized water be 100 parts by weight in terms of) artificial graphite (energy density:
It 335mAh/g) mixes with the 50wt% deionized water for accounting for ion water inventory, is stirred at normal temperature with the mixing speed of 500rpm
180min obtains mixed serum A；Weigh 1 parts by weight (by deionized water be 100 parts by weight in terms of) conductive black, 1.5 parts by weight
SBR emulsion, the mass fraction of (in terms of being 100 parts by weight by deionized water) are 0.5wt% (with artificial stone mill meter)
Mixture (the mass ratio of mixture sulfite vinyl acetate and diphenyl octyl phosphate of ethylene sulfite and diphenyl octyl phosphate
It is gone for 4- methylphthalic acid dibutyl ester and 20wt% that 6:4), mass fraction are 2wt% (with artificial stone mill meter)
Ionized water mixing, stirs 180min at normal temperature with the mixing speed of 500rpm, obtains mixed serum B；By mixed serum A and mix
Slurries B mixing is closed, 180min is stirred with the mixing speed of 500rpm at normal temperature, obtains lithium ion battery anode slurry.
Cathode pole piece preparation: the lithium ion battery anode slurry is coated uniformly on to the cathode base flow body cathode copper of 10 μ m-thicks
It on foil, is rolled after 70 DEG C of dryings with common mirror surface roller, is -0.08MPa in vacuum degree, temperature is after the completion of rolling
It is heat-treated 30min under the conditions of 150 DEG C, cathode pole piece is made.
1 performance test of test case
One, the preparation of lithium manganate battery
1, prepared by anode pole piece: in terms of the gross mass of N-N- dimethyl pyrrolidone, weighing weight fraction is 135wt%'s
Carbon nanotube CNT that conductive black that LiMn2O4, weight fraction are 3wt%, weight fraction are 1.5wt%, weight fraction are
The Kynoar and N-N- dimethyl pyrrolidone of 5wt%, mixing are stirred at normal temperature with the mixing speed of 500rpm
180min obtains lithium ion battery anode glue size；The lithium ion battery anode glue size is uniformly coated in positive base flow body pressure
Prolong on aluminium foil, is rolled after dry with common mirror surface roller, anode pole piece is made.
2, diaphragm prepares: the microporous PE diaphragm that diaphragm uses with a thickness of 25 μm.
3, prepared by electrolyte: electrolyte is dissolved into dimethyl carbonate, carbon using the hexafluoro ethylene sulfite of 1.3mol/L
Sour methyl ethyl ester, ethylene carbonate, propylene carbonate ester ORGANIC SOLVENT MIXTURES in, wherein dimethyl carbonate, methyl ethyl carbonate, carbon
Vinyl acetate, propylene carbonate ester volume ratio be (42:52:3:3), add 2wt% (with artificial stone mill meter) 1,2- carbon
Sour vinylene.
4, shell prepares: shell uses aluminum plastic film, and aluminum plastic film, which uses, has nylon layer, adhesive layer, PP with a thickness of 152 μm
Layer, adhesive layer, aluminium foil, adhesive layer, PP shape sandwich layer by layer.
5, prepared by external terminal: positive terminal uses 0.2mm thickness aluminium material tab, and negative terminal uses the nickel plating of 0.2mm copper
Tab, 3 μm of nickel coating.
6, prepared by battery: with laminar, anode pole piece, diaphragm, the alternate lamination of cathode pole piece are formed into battery core, it is unidirectional to weld
Connect tab；Then aluminum plastic film heat-sealing is carried out, electrolyte, heat-sealing sealing are injected；It successively carries out shelving-cold-hot pressure-preliminary filling-evacuation-
20Ah lithium-ion-power cell is made in chemical conversion-partial volume.Battery charging and discharging blanking voltage is 2.0~3.65V.
By lithium manganate battery cathode prepared by 1-5 of the embodiment of the present invention and battery cathode prepared by reference examples 1 according to above-mentioned
Step is prepared into battery, carries out internal driving to lithium ion battery obtained using battery Inner Resistance Tester in Virtual Instrument and tests.It will system
Standby lithium ion battery is placed on new -3000 type electrochemical property test instrument of Weir, with 0.5C current discharge, record electric discharge specific volume
Amount；With 10C current discharge, specific discharge capacity is recorded；With 15C current discharge, specific discharge capacity is recorded, voltage range 2.0~
3.65V.The lithium ion battery of preparation is placed on new -3000 type electrochemical property test instrument of Weir, with the charging of 1C electric current, with 2C
Battery discharge records its charge/discharge capacity, the cycle-index when being recycled to battery capacity to 80%, and test temperature is 45 DEG C.
Test result is shown in Table 1.
1 the performance test results of table
As seen from the above table, under the internal resistance of cell obtained by the lithium manganate battery cathode of 1-5 of embodiment of the present invention preparation is obvious
Drop, in identical discharge-rate, battery specific capacity is apparently higher than reference examples 1, and high temperature cyclic performance is obviously improved, battery electricity
Chemical property is excellent, has broad application prospects.
Those skilled in the art is not under conditions of departing from the spirit and scope of the present invention that claims determine, also
Various modifications can be carried out to the above content.Therefore the scope of the present invention is not limited in above explanation, but by
The range of claims determines.
Claims (10)
1. a kind of preparation method of lithium manganate battery cathode, which is characterized in that the negative electrode material is uniformly to apply negative electrode slurry
It overlays on Si-As-Se/C composite Nano negative electrode material copper foil, after 80 DEG C of dry 10-12h solidifications, is rolled using roller to 30-
70 μm, then obtained with sheet-punching machine punching；The negative electrode slurry is by N-methyl pyrrolidones, Si-As-Se/C composite Nano cathode material
Material, binder, thickener, conductive agent, film forming agent, pore creating material, antioxidant are made, 100-120 parts of the N-methyl pyrrolidones,
It is 80-100 parts of the Si-As-Se/C composite Nano negative electrode material, binder 5-10 parts described, thickener 5-15 parts described, described
It is 10-20 parts of conductive agent, film forming agent 5-20 parts described, pore creating material 1-10 parts described, antioxidant 5-15 parts described；
The Si-As-Se/C composite Nano negative electrode material the preparation method is as follows:
(1) it weighs suitable polyacrylonitrile to be dissolved in DMSO solution, stirs to being completely dissolved, be configured to 10% polypropylene
Nitrile/DMSO solution is added nano silica fume and continues to stir evenly；
(2) weigh acetic acid arsenic, acetic acid selenide is dissolved in DMSO, stirring is to being completely dissolved；
(3) two kinds of solution obtained in step (1) and step (2) are mixed, high-voltage electrostatic spinning, obtains nonwoven after mixing evenly
Cloth film, as pre-oxidizing 2-5h in air, in 270 DEG C of heating rate low-temperature bake 5h with 5 DEG C/min, Ar gas bar part down toward
In 400-600 DEG C of high-temperature calcination 3-6h of Muffle furnace, it is made after carbonization；
The ratio between amount of substance of the acetic acid arsenic, acetic acid selenide and nano silica fume is 3:2:10；
The negative electrode slurry the preparation method is as follows: by Si-As-Se/C composite Nano negative electrode material, binder, thickener, leading
Electric agent, antioxidant are dissolved in N-methyl pyrrolidones, and ultrasonic mixing dissolution stirs evenly, pore creating material is added, is warming up to 70 DEG C,
Stirring and dissolving is added film forming agent, rises to 85 DEG C, stir evenly, be cooled to room temperature, obtain gluey slurries, is made.
2. a kind of preparation method of lithium manganate battery cathode according to claim 1, which is characterized in that the high-pressure electrostatic is spun
Silk step condition is voltage 15KV, and temperature is 30-40 DEG C, drum rotation speed 50r/min, and solidification distance is 10-12cm.
3. a kind of preparation method of lithium manganate battery cathode according to claim 1, which is characterized in that the negative electrode slurry by
Following raw material is prepared: 105-112 parts of N-methyl pyrrolidones, Si-As-Se/C composite Nano negative electrode material 85-
93 parts, 7-9 parts of binder, 7-12 parts of thickener, 12-17 parts of conductive agent, 9-15 parts of film forming agent, 3-7 parts of pore creating material, antioxidant 8-
13 parts.
4. a kind of preparation method of lithium manganate battery cathode according to claim 3, which is characterized in that the negative electrode slurry by
Following raw material is prepared: 110 parts of N-methyl pyrrolidones, glues at 89 parts of Si-As-Se/C composite Nano negative electrode material
Tie 8 parts of agent, 9 parts of thickener, 15 parts of conductive agent, 13 parts of film forming agent, 6 parts of pore creating material, 12 parts of antioxidant.
5. a kind of preparation method of lithium manganate battery cathode according to claim 1, which is characterized in that the binder is selected from
One of polyvinyl alcohol, LA132, polytetrafluoroethylene (PTFE), polyurethane, sodium carboxymethylcellulose or Viton.
6. a kind of preparation method of lithium manganate battery cathode according to claim 1, which is characterized in that the thickener is selected from
Methylcellulose, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl methyl cellulose, acrylic acid, methacrylic acid, poly- third
Acrylamide, polyvinyl alcohol, polyvinylpyrrolidone, polyethylene glycol oxide, carbomer, polyacrylic acid, Sodium Polyacrylate, suitable fourth rubber
One or more of glue, butadiene-styrene rubber, polyurethane, modified polyurea or low-molecular polyethylene wax.
7. a kind of preparation method of lithium manganate battery cathode according to claim 1, which is characterized in that the conductive agent is selected from
One or more of acetylene black, Super P, Super S, 350G, carbon fiber, carbon nanotube or Ketjen black.
8. a kind of preparation method of lithium manganate battery cathode according to claim 1, which is characterized in that the film forming agent is nitre
Sour fiber film forming agent.
9. a kind of preparation method of lithium manganate battery cathode according to claim 1, which is characterized in that the pore creating material is selected from
One of PS microballoon, PMMA microsphere, ceramic microbead, coal dust or carbon black.
10. a kind of preparation method of lithium manganate battery cathode according to claim 1, which is characterized in that the antioxidant choosing
From diphenylamines, p-phenylenediamine, dihydroquinoline, 2,6- three-level butyl -4- methylphenol, bis- (3,5- three-level butyl -4- hydroxy benzenes
Base) one or more of thioether or four (β-(3,5- three-level butyl -4- hydroxy phenyl) propionic acid) pentaerythritol esters.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811172095.XA CN109301218A (en) | 2018-10-09 | 2018-10-09 | A kind of preparation method of lithium manganate battery cathode |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811172095.XA CN109301218A (en) | 2018-10-09 | 2018-10-09 | A kind of preparation method of lithium manganate battery cathode |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109301218A true CN109301218A (en) | 2019-02-01 |
Family
ID=65161766
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811172095.XA Pending CN109301218A (en) | 2018-10-09 | 2018-10-09 | A kind of preparation method of lithium manganate battery cathode |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109301218A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110993884A (en) * | 2019-12-06 | 2020-04-10 | 联动天翼新能源有限公司 | Lithium ion battery negative electrode slurry, preparation method, negative electrode plate and battery |
| CN111411450A (en) * | 2020-02-17 | 2020-07-14 | 五邑大学 | A kind of preparation method and application of flexible nano-cobweb structure conductive polyurethane film |
| CN112751030A (en) * | 2019-10-31 | 2021-05-04 | 苏州微木智能系统有限公司 | Negative pole piece and lithium ion battery thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103305965A (en) * | 2013-06-04 | 2013-09-18 | 清华大学深圳研究生院 | Silicon-carbon composite material with nano micropores and preparation method as well as application thereof |
| CN104659343A (en) * | 2013-11-19 | 2015-05-27 | 三星Sdi株式会社 | Negative active material and negative electrode and lithium battery containing the material, and method of manufacturing the same |
| US20160197343A1 (en) * | 2015-01-07 | 2016-07-07 | Samsung Sdi Co., Ltd. | Secondary battery |
| CN107749459A (en) * | 2016-11-07 | 2018-03-02 | 万向二三股份公司 | A kind of preparation method of lithium manganate battery negative pole |
-
2018
- 2018-10-09 CN CN201811172095.XA patent/CN109301218A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103305965A (en) * | 2013-06-04 | 2013-09-18 | 清华大学深圳研究生院 | Silicon-carbon composite material with nano micropores and preparation method as well as application thereof |
| CN104659343A (en) * | 2013-11-19 | 2015-05-27 | 三星Sdi株式会社 | Negative active material and negative electrode and lithium battery containing the material, and method of manufacturing the same |
| US20160197343A1 (en) * | 2015-01-07 | 2016-07-07 | Samsung Sdi Co., Ltd. | Secondary battery |
| CN107749459A (en) * | 2016-11-07 | 2018-03-02 | 万向二三股份公司 | A kind of preparation method of lithium manganate battery negative pole |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112751030A (en) * | 2019-10-31 | 2021-05-04 | 苏州微木智能系统有限公司 | Negative pole piece and lithium ion battery thereof |
| CN110993884A (en) * | 2019-12-06 | 2020-04-10 | 联动天翼新能源有限公司 | Lithium ion battery negative electrode slurry, preparation method, negative electrode plate and battery |
| CN110993884B (en) * | 2019-12-06 | 2021-07-23 | 联动天翼新能源有限公司 | Lithium ion battery negative electrode slurry, preparation method, negative electrode plate and battery |
| CN111411450A (en) * | 2020-02-17 | 2020-07-14 | 五邑大学 | A kind of preparation method and application of flexible nano-cobweb structure conductive polyurethane film |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111900388B (en) | Zinc ion battery negative electrode material, preparation and application thereof | |
| CN102800841B (en) | Negative plate, lithium ion battery and preparation method thereof | |
| CN109638212A (en) | A high-rate fast-charge lithium-ion battery | |
| CN106654235A (en) | Composite graphite material and preparation method thereof and lithium-ion battery comprising composite graphite material | |
| CN108767242A (en) | It is a kind of can prelithiation lithium ion start and stop power supply and preparation method thereof | |
| CN107978794A (en) | The lithium battery electric core of ternary lithium battery electrolytes and high temperature resistant high power capacity high safety | |
| CN102709597A (en) | Composite all solid-state polymer electrolyte lithium ion battery and preparation method of composite all solid-state polymer electrolyte lithium ion battery | |
| CN105742695B (en) | A kind of lithium ion battery and preparation method thereof | |
| CN104934579A (en) | Preparation method for porous graphite doped and carbon coated graphite anode material | |
| CN101916848A (en) | LiFePO4 coating LiMn2O4 composite electrode material and preparation method thereof | |
| CN103928668B (en) | Lithium ion battery and preparation method of anode material thereof | |
| CN102983368B (en) | Preparation method of high-temperature NI-MH power battery | |
| CN106887575A (en) | A kind of cobalt acid zinc/graphene composite negative pole and preparation method thereof and lithium ion battery | |
| CN109686920A (en) | A kind of high-energy density anode pole piece and its preparation method and application | |
| CN109698334A (en) | Positive plate, lithium titanate battery and preparation method thereof | |
| CN106684343A (en) | Lithium titanate/carbon composite material and preparation method therefor, and lithium ion battery | |
| CN109301218A (en) | A kind of preparation method of lithium manganate battery cathode | |
| CN106784855A (en) | A kind of unmanned plane manufacture method of high temperature modification lithium ion battery | |
| WO2023087209A1 (en) | Electrochemical device and electronic device | |
| CN110112366A (en) | A kind of electrodes of lithium-ion batteries and lithium ion battery | |
| CN110364681A (en) | A kind of based lithium-ion battery positive plate of the high security of triple protection | |
| CN106654276A (en) | Preparation method of solid-state lithium ion battery electrode taking PEO (Polyethylene Oxide) as binding agent | |
| CN112614703A (en) | Negative electrode material of ionic capacitor and preparation method and application thereof | |
| CN115986122A (en) | Electrode plate of water-based sodium-ion battery, battery and preparation method of electrode plate and battery | |
| CN110311167A (en) | A kind of composite solid electrolyte sheet and its preparation method and solid-state battery |
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 | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190201 |
|
| RJ01 | Rejection of invention patent application after publication |