CN109119619B - A kind of preparation method of the lithium ion cell positive of high rate capability - Google Patents
A kind of preparation method of the lithium ion cell positive of high rate capability Download PDFInfo
- Publication number
- CN109119619B CN109119619B CN201811038433.0A CN201811038433A CN109119619B CN 109119619 B CN109119619 B CN 109119619B CN 201811038433 A CN201811038433 A CN 201811038433A CN 109119619 B CN109119619 B CN 109119619B
- Authority
- CN
- China
- Prior art keywords
- stirred under
- under vacuum
- added
- active material
- material layer
- 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
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
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- 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
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- 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
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- 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 present invention provides a kind of preparation methods of the lithium ion cell positive of high rate capability, the anode includes collector and the first active material layer, the second active material layer and passivation conductive layer on collector, first active material layer includes lithium nickel oxide, second active material layer includes the lithium manganese cobalt/cobalt oxide of doping and the LiFePO4 of doping, and the passivation conductive layer includes inorganic oxide particles and organic conductive polymer.Preparation method of the invention, by controlling production technology, so that conductivity height is obtained, and stable structure, the anode of good cycle under high magnification environment.
Description
Technical field
The present invention relates to technical field of lithium ion, more particularly to a kind of lithium ion cell positive of high rate capability
Preparation method.
Background technique
It is single as electric tool is gradually increased to what the energy density of battery, output power and cycle life required
The anode that active material is constituted is no longer satisfied the demand of electric tool, and the battery of blended anode material becomes research and development at present
Emphasis, and it is directed to different materials, different mixing technologies and the structure design different for active material are needed, and it is current
Mixing material be although capable of providing higher output power and energy density, but cause since the degree of compression of pole piece is excessive
The internal resistance of pole piece is bigger than normal, and heat release is obvious under high magnification, and since the transition metal Ni cycle life for dissolving out caused battery becomes
Difference.
Summary of the invention
In order to solve above-mentioned problems of the prior art, the present invention provides a kind of lithium-ion electrics of high rate capability
The preparation method of pond anode, the anode include collector and the first active material layer on collector, the second activity
Material layer and passivation conductive layer, first active material layer includes lithium nickel oxide, and second active material layer includes mixing
The LiFePO4 of miscellaneous lithium manganese cobalt/cobalt oxide and doping, the passivation conductive layer include that inorganic oxide particles and organic conductive are poly-
Close object.Preparation method of the invention, by controlling production technology, to obtain conductivity height, stable structure, under high magnification environment
The anode of good cycle.
Specific scheme is as follows:
A kind of preparation method of the lithium ion cell positive of high rate capability, the anode is including collector and is located at collection
The first active material layer, the second active material layer and passivation conductive layer on fluid, first active material layer includes lithium nickel
Oxide, second active material layer include the lithium manganese cobalt/cobalt oxide of doping and the LiFePO4 of doping, and the passivation is conductive
Layer includes inorganic oxide particles and organic conductive polymer, including following steps:
1) lithium nickel oxide, is provided, the molecular formula of the lithium nickel oxide is LiNixCoyMzO2, wherein M is selected from Nb, Ti；
X+y+z=1, x >=0.7, y >=0.15,0.01≤z≤0.03；The average grain diameter of the lithium nickel oxide is 500-2000nm, long
Diameter ratio is 1.0-1.2, and the lithium nickel oxide is mixed with conductive carbon black with the mass ratio of 100:3-6, is placed in ball grinder, with
The revolving speed ball milling 6-8h of 200-300r/min；
2), solvent is added in the first vacuum stirring kettle, binder is added in the first vacuum stirring kettle, vacuum is stirred
2-4h is mixed, dispersing agent is added, is stirred under vacuum 1-2h, the product of step 1 is added, is stirred under vacuum 4-6h, addition length is 5-20
The carbon nano-fiber of micron is stirred under vacuum 4-6h, obtains the first slurry, wherein mass ratio, the lithium nickel oxide: conductive carbon
It is black: binder: dispersing agent: carbon nano-fiber=100:3-6:4-8:2-4:5-8；
3), the lithium manganese cobalt/cobalt oxide of doping and the LiFePO4 of doping, point of the lithium manganese cobalt/cobalt oxide of the doping are provided
Minor is LiMnxCoyMzO2, wherein M is selected from Mg, Al；X+y+z=1, x >=0.5, y >=0.3,0.01≤z≤0.03；The lithium
The average grain diameter of manganese cobalt/cobalt oxide is 1-3 microns, draw ratio 1.5-2.5；The molecular formula of the LiFePO4 of the doping is
LiFexMzPO4, wherein M is selected from Nb, Mg；X+z=1,0.02≤z≤0.03；The average grain diameter of the LiFePO4 is 100-
300nm, draw ratio 1.0-1.2；By the lithium manganese cobalt/cobalt oxide, the LiFePO4 and conductive carbon black with 100:40-60:3-
6 mass ratio mixing, is placed in ball grinder, with the revolving speed ball milling 6-8h of 200-300r/min；
4), solvent is added in the second vacuum stirring kettle, binder is added in the second vacuum stirring kettle, vacuum is stirred
2-4h is mixed, dispersing agent is added, is stirred under vacuum 1-2h, the product of step 3 is added, 4-6h is stirred under vacuum, obtains the second slurry,
Middle mass ratio, the lithium manganese cobalt/cobalt oxide: the LiFePO4: conductive carbon black: binder: dispersing agent=100:40-60:3-6:
3-5:2-4；
5) solvent, is added to third to be stirred under vacuum in kettle, binder is added to third and is stirred under vacuum in kettle, vacuum is stirred
2-4h is mixed, dispersing agent is added, is stirred under vacuum 1-2h, inorganic oxide particles are added, is stirred under vacuum 4-6h, organic conductive is added
Polymer is stirred under vacuum 4-6h, obtains third slurry, wherein mass ratio, inorganic oxide particles: organic conductive polymer: viscous
Tie agent: dispersing agent=100:70-150:2-4:3-5；
6), collector is provided, on a current collector by the coating of the first slurry, dry, hot pressing obtains the first active material layer, then
Second slurry is coated on the first active material layer, dry, hot pressing obtains the second active material layer；Third slurry is coated with again
Dry on the second active material layer, hot pressing obtains the anode.
Further, first slurry and the second slurry solid content are independently 50-54%.
Further, the solid content of the third slurry is 56-60%.
Further, the conductive carbon black is acetylene black.
Further, the dispersing agent is sodium carboxymethylcellulose.
Further, in step 6, the pressure of hot pressing is successively reduced three times.
Further, the first layer, the second layer, the thickness ratio of third layer are 6-10:40-60:2-4.
Further, the organic conductive polymer is polypyrrole.
The invention has the following beneficial effects:
1), the lithium nickel oxide with high electrical conductivity improves active material layer as the first layer contacted with collector
With the conductivity of collector, and the high material of nickel content is easy nickel dissolution, leads to active material performance degradation, is set to
First layer far from electrolyte interface, can be improved the stability of electrode active material；Simultaneously by itself and conductive carbon before mixing
Black ball mill, improves the contact area of conductive carbon black and active material, improves conductivity；
2), the second layer is by the mixed layer of setting multiple material, by two kinds of active materials of ball milling before slurrying, after ball milling
The the second active material layer surface density with higher and energy density that active material is constituted, structural stability is higher, while the
Ni element is free of in two layers, and the Ni of first layer can be stopped to dissolve out, improve the cycle life of electrode；
3), the inorganic oxide of third layer can be magnesia, aluminium oxide, zirconium oxide etc., in electrode active material and electricity
Passivation layer is formed between solution liquid, avoids the dissolution of transition metal and the decomposition of electrolyte, conducting polymer, which is added, reduces electrode
Resistance；Polypyrrole in third layer, the conjugated electrons pair with hetero-aromatic ring can hinder the dissolution of transition metal, improve
The cycle performance of electrode；
4), trilaminate material is gradually reduced by different pressure, pressure, to make the compacted density of trilaminate material by introversion
It gradually reduces outside, can be improved electrolyte to the effect of impregnation of electrode；
5), first layer and third layer use the carbon nano-fiber of specific length range, and conductive network is formed in layer, reduce
Resistance in layer, and the mechanical performance of layer is improved, it can be avoided active material and fall off；
6), inventor determines the structural parameters of a variety of materials by trial and test many times, so that electrode is with low
Resistance, high structural stability and cyclic durability.
Specific embodiment
The present invention will be described in more detail below by specific embodiment, but protection scope of the present invention not by
It is limited to these embodiments.
Embodiment 1
1) lithium nickel oxide, is provided, the molecular formula of the lithium nickel oxide is LiNi0.7Co0.29Nb0.01O2；The lithium nickel
The average grain diameter of oxide is 500nm, and draw ratio 1.0 mixes the lithium nickel oxide and acetylene black with the mass ratio of 100:3
It closes, is placed in ball grinder, with the revolving speed ball milling 6h of 200r/min；
2), solvent is added in the first vacuum stirring kettle, PVDF is added in the first vacuum stirring kettle, is stirred under vacuum
2h adds sodium carboxymethylcellulose, is stirred under vacuum 1h, and the product of step 1 is added, and is stirred under vacuum 4h, and it is 5 microns that length, which is added,
Carbon nano-fiber, be stirred under vacuum 4h, obtain the first slurry, the solid content of first slurry is 50%, wherein mass ratio, institute
State lithium nickel oxide: acetylene black: PVDF: sodium carboxymethylcellulose: carbon nano-fiber=100:3:4:2:5；
3), the lithium manganese cobalt/cobalt oxide of doping and the LiFePO4 of doping, point of the lithium manganese cobalt/cobalt oxide of the doping are provided
Minor is LiMn0.5Co0.49Mg0.1O2；The average grain diameter of the lithium manganese cobalt/cobalt oxide is 1 micron, draw ratio 1.5；The doping
LiFePO4 molecular formula be LiFe0.98Nb0.02PO4；The average grain diameter of the LiFePO4 is 100nm, draw ratio 1.0；
The lithium manganese cobalt/cobalt oxide, the LiFePO4 are mixed with acetylene black with the mass ratio of 100:40:3, are placed in ball grinder, with
The revolving speed ball milling 6h of 200r/min；
4), solvent is added in the second vacuum stirring kettle, PVDF is added in the second vacuum stirring kettle, is stirred under vacuum
2h adds sodium carboxymethylcellulose, is stirred under vacuum 1h, and the product of step 3 is added, and is stirred under vacuum 4h, obtains the second slurry, institute
Stating the second slurry solid content is 50%, wherein mass ratio, the lithium manganese cobalt/cobalt oxide: the LiFePO4: acetylene black: PVDF:
Sodium carboxymethylcellulose=100:40:3:3:2；
5) solvent, is added to third to be stirred under vacuum in kettle, PVDF is added to third and is stirred under vacuum in kettle, is stirred under vacuum
2h adds sodium carboxymethylcellulose, is stirred under vacuum 1h, and the aluminum oxide particle that partial size is 200nm is added, is stirred under vacuum
Polypyrrole is added in 4h, is stirred under vacuum 4h, obtains third slurry, and the solid content of the third slurry is 56%, wherein mass ratio,
Aluminum oxide particle: polypyrrole: PVDF: sodium carboxymethylcellulose=100:70:2:3；
6) collector, is provided, on a current collector by the coating of the first slurry, 100 DEG C of dryings, 0.15MPa hot pressing obtains first
Active material layer, then the second slurry is coated on the first active material layer, 100 DEG C of dryings, it is living that 0.14MPa hot pressing obtains second
Property material layer；Third slurry is coated on the second active material layer again, 100 DEG C of dryings, 0.13MPa hot pressing obtains third layer,
The first layer, the second layer, the thickness ratio 6:40:2 of third layer obtain the anode.
Embodiment 2
1) lithium nickel oxide, is provided, the molecular formula of the lithium nickel oxide is LiNi0.82Co0.15Ti0.03O2；The lithium nickel
The average grain diameter of oxide is 2000nm, draw ratio 1.2, by the lithium nickel oxide and acetylene black with the mass ratio of 100:6
Mixing, is placed in ball grinder, with the revolving speed ball milling 8h of 300r/min；
2), solvent is added in the first vacuum stirring kettle, PVDF is added in the first vacuum stirring kettle, is stirred under vacuum
4h adds sodium carboxymethylcellulose, is stirred under vacuum 2h, and the product of step 1 is added, and is stirred under vacuum 6h, and it is 20 micro- that length, which is added,
The carbon nano-fiber of rice is stirred under vacuum 6h, obtains the first slurry, and the solid content of first slurry is 54%, wherein mass ratio,
The lithium nickel oxide: acetylene black: PVDF: sodium carboxymethylcellulose: carbon nano-fiber=100:6:8:4:8；
3), the lithium manganese cobalt/cobalt oxide of doping and the LiFePO4 of doping, point of the lithium manganese cobalt/cobalt oxide of the doping are provided
Minor is LiMn0.67Co0.3Al0.03O2；The average grain diameter of the lithium manganese cobalt/cobalt oxide is 3 microns, draw ratio 2.5；It is described to mix
The molecular formula of miscellaneous LiFePO4 is LiFe0.97Mg0.03PO4；The average grain diameter of the LiFePO4 is 300nm, and draw ratio is
1.2；The lithium manganese cobalt/cobalt oxide, the LiFePO4 are mixed with acetylene black with the mass ratio of 100:60:6, ball grinder is placed in
In, with the revolving speed ball milling 8h of 300r/min；
4), solvent is added in the second vacuum stirring kettle, PVDF is added in the second vacuum stirring kettle, is stirred under vacuum
4h adds sodium carboxymethylcellulose, is stirred under vacuum 2h, and the product of step 3 is added, and is stirred under vacuum 6h, obtains the second slurry, institute
Stating the second slurry solid content is 54%, wherein mass ratio, the lithium manganese cobalt/cobalt oxide: the LiFePO4: acetylene black: PVDF:
Sodium carboxymethylcellulose=100:60:6:5:4；
5) solvent, is added to third to be stirred under vacuum in kettle, PVDF is added to third and is stirred under vacuum in kettle, is stirred under vacuum
4h adds sodium carboxymethylcellulose, is stirred under vacuum 2h, and the aluminum oxide particle that partial size is 200nm is added, is stirred under vacuum
Polypyrrole is added in 6h, is stirred under vacuum 6h, obtains third slurry, and the solid content of the third slurry is 60%, wherein mass ratio,
Aluminum oxide particle: polypyrrole: PVDF: sodium carboxymethylcellulose=100:150:4:5；
6) collector, is provided, on a current collector by the coating of the first slurry, 100 DEG C of dryings, 0.15MPa hot pressing obtains first
Active material layer, then the second slurry is coated on the first active material layer, 100 DEG C of dryings, it is living that 0.14MPa hot pressing obtains second
Property material layer；Third slurry is coated on the second active material layer again, 100 DEG C of dryings, 0.13MPa hot pressing obtains third layer,
The first layer, the second layer, the thickness ratio 10:60:4 of third layer obtain the anode.
Embodiment 3
1) lithium nickel oxide, is provided, the molecular formula of the lithium nickel oxide is LiNi0.7Co0.29Nb0.01O2；The lithium nickel
The average grain diameter of oxide is 1000nm, draw ratio 1.2, by the lithium nickel oxide and acetylene black with the mass ratio of 100:5
Mixing, is placed in ball grinder, with the revolving speed ball milling 8h of 300r/min；
2), solvent is added in the first vacuum stirring kettle, PVDF is added in the first vacuum stirring kettle, is stirred under vacuum
4h adds sodium carboxymethylcellulose, is stirred under vacuum 2h, and the product of step 1 is added, and is stirred under vacuum 6h, and it is 10 micro- that length, which is added,
The carbon nano-fiber of rice is stirred under vacuum 6h, obtains the first slurry, and the solid content of first slurry is 52%, wherein mass ratio,
The lithium nickel oxide: acetylene black: PVDF: sodium carboxymethylcellulose: carbon nano-fiber=100:5:6:3:7；
3), the lithium manganese cobalt/cobalt oxide of doping and the LiFePO4 of doping, point of the lithium manganese cobalt/cobalt oxide of the doping are provided
Minor is LiMn0.67Co0.3Al0.03O2；The average grain diameter of the lithium manganese cobalt/cobalt oxide is 2 microns, draw ratio 2.0；It is described to mix
The molecular formula of miscellaneous LiFePO4 is LiFe0.97Mg0.03PO4；The average grain diameter of the LiFePO4 is 200nm, and draw ratio is
1.1；The lithium manganese cobalt/cobalt oxide, the LiFePO4 are mixed with acetylene black with the mass ratio of 100:50:5, ball grinder is placed in
In, with the revolving speed ball milling 8h of 300r/min；
4), solvent is added in the second vacuum stirring kettle, PVDF is added in the second vacuum stirring kettle, is stirred under vacuum
4h adds sodium carboxymethylcellulose, is stirred under vacuum 2h, and the product of step 3 is added, and is stirred under vacuum 6h, obtains the second slurry, institute
Stating the second slurry solid content is 52%, wherein mass ratio, the lithium manganese cobalt/cobalt oxide: the LiFePO4: acetylene black: PVDF:
Sodium carboxymethylcellulose=100:50:4:4:3；
5) solvent, is added to third to be stirred under vacuum in kettle, PVDF is added to third and is stirred under vacuum in kettle, is stirred under vacuum
4h adds sodium carboxymethylcellulose, is stirred under vacuum 2h, and the aluminum oxide particle that partial size is 200nm is added, is stirred under vacuum
Polypyrrole is added in 6h, is stirred under vacuum 6h, obtains third slurry, and the solid content of the third slurry is 58%, wherein mass ratio,
Aluminum oxide particle: polypyrrole: PVDF: sodium carboxymethylcellulose=100:100:3:4；
6) collector, is provided, on a current collector by the coating of the first slurry, 100 DEG C of dryings, 0.15MPa hot pressing obtains first
Active material layer, then the second slurry is coated on the first active material layer, 100 DEG C of dryings, it is living that 0.14MPa hot pressing obtains second
Property material layer；Third slurry is coated on the second active material layer again, 100 DEG C of dryings, 0.13MPa hot pressing obtains third layer,
The first layer, the second layer, the thickness ratio 8:50:3 of third layer obtain the anode.
Embodiment 4
1) lithium nickel oxide, is provided, the molecular formula of the lithium nickel oxide is LiNi0.82Co0.15Ti0.03O2；The lithium nickel
The average grain diameter of oxide is 1000nm, draw ratio 1.1, by the lithium nickel oxide and acetylene black with the quality of 100:3-6
Than mixing, it is placed in ball grinder, with the revolving speed ball milling 8h of 300r/min；
2), solvent is added in the first vacuum stirring kettle, PVDF is added in the first vacuum stirring kettle, is stirred under vacuum
4h adds sodium carboxymethylcellulose, is stirred under vacuum 2h, and the product of step 1 is added, and is stirred under vacuum 6h, and it is 15 micro- that length, which is added,
The carbon nano-fiber of rice is stirred under vacuum 6h, obtains the first slurry, and the solid content of first slurry is 54%, wherein mass ratio,
The lithium nickel oxide: acetylene black: PVDF: sodium carboxymethylcellulose: carbon nano-fiber=100:5:6:4:8；
3), the lithium manganese cobalt/cobalt oxide of doping and the LiFePO4 of doping, point of the lithium manganese cobalt/cobalt oxide of the doping are provided
Minor is LiMn0.5Co0.49Mg0.1O2；The average grain diameter of the lithium manganese cobalt/cobalt oxide is 3 microns, draw ratio 2.5；The doping
LiFePO4 molecular formula be LiFe0.98Nb0.02PO4；The average grain diameter of the LiFePO4 is 200nm, draw ratio 1.2；
The lithium manganese cobalt/cobalt oxide, the LiFePO4 are mixed with acetylene black with the mass ratio of 100:50:6, are placed in ball grinder, with
The revolving speed ball milling 8h of 300r/min；
4), solvent is added in the second vacuum stirring kettle, PVDF is added in the second vacuum stirring kettle, is stirred under vacuum
4h adds sodium carboxymethylcellulose, is stirred under vacuum 2h, and the product of step 3 is added, and is stirred under vacuum 6h, obtains the second slurry, institute
Stating the second slurry solid content is 54%, wherein mass ratio, the lithium manganese cobalt/cobalt oxide: the LiFePO4: acetylene black: PVDF:
Sodium carboxymethylcellulose=100:60:6:5:4；
5) solvent, is added to third to be stirred under vacuum in kettle, PVDF is added to third and is stirred under vacuum in kettle, is stirred under vacuum
4h adds sodium carboxymethylcellulose, is stirred under vacuum 2h, and the aluminum oxide particle that partial size is 200nm is added, is stirred under vacuum
Polypyrrole is added in 6h, is stirred under vacuum 6h, obtains third slurry, and the solid content of the third slurry is 60%, wherein mass ratio,
Aluminum oxide particle: polypyrrole: PVDF: sodium carboxymethylcellulose=100:120:4:4；
6) collector, is provided, on a current collector by the coating of the first slurry, 100 DEG C of dryings, 0.15MPa hot pressing obtains first
Active material layer, then the second slurry is coated on the first active material layer, 100 DEG C of dryings, it is living that 0.14MPa hot pressing obtains second
Property material layer；Third slurry is coated on the second active material layer again, 100 DEG C of dryings, 0.13MPa hot pressing obtains third layer,
The first layer, the second layer, the thickness ratio of third layer: 8:50:3 obtains the anode.
Comparative example 1
The first active material, the second active material and third active material are provided, wherein the molecular formula of the first active material
For LiNi0.8Mn0.1Co0.1O2, the molecular formula of the second active material is LiNi0.3Mn0.4Co0.3O2, third active material is
LiMnPO4；Each active material is added in NMP according to mass ratio 1:1:1,3% PVDF, 4% Super P is added, and
3% sodium carboxymethylcellulose, it is that 50%, 50r/min vacuum stirring 12h obtains slurry that NMP adjustment solid-to-liquid ratio, which is added, provides collection
Fluid, on a current collector by slurry coating, 100 DEG C of dryings, hot pressing (pressure is 0.15 megapascal) obtain anode.
Test and result
Embodiment 1-4 and the anode of comparative example 1 and lithium metal reference electrode composition test cell, due to battery electrode activity
The amount of material cannot keep identical, and capacity retention ratio is the suitable parameters for measuring life performance, the appearance recycled under 1C, 2C
Amount conservation rate is shown in Table 1, and the decaying of conservation rate under the cycle life of the battery of embodiment 1-4 especially high magnification is lower, follows for 100 times
Capacity retention ratio after ring is apparently higher than the anode of comparative example 1.
Table 1
It is discussed in detail although the contents of the present invention have passed through above preferred embodiment, but it would be recognized that above-mentioned
Description be not considered as limitation of the present invention.
Claims (8)
1. a kind of preparation method of the lithium ion cell positive of high rate capability, the anode is including collector and is located at afflux
The first active material layer, the second active material layer and passivation conductive layer on body, first active material layer includes lithium nickel oxygen
Compound, second active material layer include the lithium manganese cobalt/cobalt oxide of doping and the LiFePO4 of doping, the passivation conductive layer
Including inorganic oxide particles and organic conductive polymer, including following steps:
1) lithium nickel oxide, is provided, the molecular formula of the lithium nickel oxide is LiNixCoyMzO2, wherein M is selected from Nb, Ti；x+y+z
=1, x >=0.7, y >=0.15,0.01≤z≤0.03；The average grain diameter of the lithium nickel oxide is 500-2000nm, draw ratio
For 1.0-1.2, the lithium nickel oxide is mixed with conductive carbon black with the mass ratio of 100:3-6, is placed in ball grinder, with 200-
The revolving speed ball milling 6-8h of 300r/min；
2), solvent is added in the first vacuum stirring kettle, binder is added in the first vacuum stirring kettle, is stirred under vacuum 2-
4h adds dispersing agent, is stirred under vacuum 1-2h, and the product of step 1 is added, and is stirred under vacuum 4-6h, and it is 5-20 microns that length, which is added,
Carbon nano-fiber, be stirred under vacuum 4-6h, obtain the first slurry, wherein mass ratio, the lithium nickel oxide: conductive carbon black: viscous
Tie agent: dispersing agent: carbon nano-fiber=100:3-6:4-8:2-4:5-8；
3), the lithium manganese cobalt/cobalt oxide of doping and the LiFePO4 of doping, the molecular formula of the lithium manganese cobalt/cobalt oxide of the doping are provided
For LiMnxCoyMzO2, wherein M is selected from Mg, Al；X+y+z=1, x >=0.5, y >=0.3,0.01≤z≤0.03；The lithium manganese cobalt
The average grain diameter of oxide is 1-3 microns, draw ratio 1.5-2.5；The molecular formula of the LiFePO4 of the doping is
LiFexMzPO4, wherein M is selected from Nb, Mg；X+z=1,0.02≤z≤0.03；The average grain diameter of the LiFePO4 is 100-
300nm, draw ratio 1.0-1.2；By the lithium manganese cobalt/cobalt oxide, the LiFePO4 and conductive carbon black with 100:40-60:3-
6 mass ratio mixing, is placed in ball grinder, with the revolving speed ball milling 6-8h of 200-300r/min；
4), solvent is added in the second vacuum stirring kettle, binder is added in the second vacuum stirring kettle, is stirred under vacuum 2-
4h adds dispersing agent, is stirred under vacuum 1-2h, and the product of step 3 is added, and is stirred under vacuum 4-6h, obtains the second slurry, wherein matter
Ratio is measured, the lithium manganese cobalt/cobalt oxide: the LiFePO4: conductive carbon black: binder: dispersing agent=100:40-60:3-6:3-5:
2-4；
5) solvent, is added to third to be stirred under vacuum in kettle, binder is added to third and is stirred under vacuum in kettle, 2- is stirred under vacuum
4h adds dispersing agent, is stirred under vacuum 1-2h, and inorganic oxide particles are added, and is stirred under vacuum 4-6h, and organic conductive polymerization is added
Object is stirred under vacuum 4-6h, obtains third slurry, wherein mass ratio, inorganic oxide particles: organic conductive polymer: binder:
Dispersing agent=100:70-150:2-4:3-5；
6), collector is provided, on a current collector by the coating of the first slurry, dry, first time hot pressing obtains the first active material layer,
The second slurry is coated on the first active material layer again, dry, second of hot pressing obtains the second active material layer；Again by third
Slurry is coated on the second active material layer, dry, and third time hot pressing obtains the anode.
2. first slurry and the second slurry solid content are independently 50-54% such as above-mentioned method described in claim 1.
3. the solid content of the third slurry is 56-60% such as above-mentioned method described in claim 1.
4. the conductive carbon black is acetylene black such as the claims 1-3 described in any item methods.
5. the dispersing agent is sodium carboxymethylcellulose such as the claims 1-3 described in any item methods.
6. in step 6, the pressure of hot pressing is successively reduced three times such as the claims 1-3 described in any item methods.
7. such as the described in any item methods of the claims 1-3, first active material layer, the second active material layer are blunt
The thickness ratio for changing conductive layer is 6-10:40-60:2-4.
8. the organic conductive polymer is polypyrrole such as the claims 1-3 described in any item methods.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811038433.0A CN109119619B (en) | 2018-09-06 | 2018-09-06 | A kind of preparation method of the lithium ion cell positive of high rate capability |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811038433.0A CN109119619B (en) | 2018-09-06 | 2018-09-06 | A kind of preparation method of the lithium ion cell positive of high rate capability |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109119619A CN109119619A (en) | 2019-01-01 |
| CN109119619B true CN109119619B (en) | 2019-11-19 |
Family
ID=64858926
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811038433.0A Active CN109119619B (en) | 2018-09-06 | 2018-09-06 | A kind of preparation method of the lithium ion cell positive of high rate capability |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109119619B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110010873B (en) * | 2019-04-09 | 2020-09-04 | 江西迪比科股份有限公司 | Preparation method of mixed anode slurry |
| CN110416496B (en) * | 2019-08-05 | 2020-12-11 | 泰州纳新新能源科技有限公司 | Cathode slurry and preparation method of cathode |
| CN110571406B (en) * | 2019-09-12 | 2020-12-15 | 泰州纳新新能源科技有限公司 | Preparation method of carbon material cathode for lithium ion battery |
| CN110707293B (en) * | 2019-10-15 | 2020-12-11 | 泰州纳新新能源科技有限公司 | Preparation method of lithium ion battery cathode |
| CN110676428B (en) * | 2019-10-17 | 2020-12-15 | 泰州纳新新能源科技有限公司 | Preparation method of mixed anode for lithium ion battery |
| CN111276757B (en) * | 2020-02-19 | 2021-01-05 | 苏州睿邦工业设计有限公司 | Preparation method of power type lithium ion battery |
| CN111900328A (en) * | 2020-06-22 | 2020-11-06 | 珠海冠宇电池股份有限公司 | Positive plate and lithium ion battery containing same |
| EP4120408A4 (en) | 2020-08-14 | 2023-06-07 | Contemporary Amperex Technology Co., Limited | Secondary battery and preparation method therefor, and battery module, battery pack, and apparatus comprising secondary battery |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102891299A (en) * | 2012-09-12 | 2013-01-23 | 黎军 | High-rate lithium ion battery cathode material and preparation method and application thereof |
| CN106450199A (en) * | 2016-10-24 | 2017-02-22 | 东莞市联洲知识产权运营管理有限公司 | Preparation method of safe and environment-friendly high-rate lithium-ion battery |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102386379A (en) * | 2011-10-19 | 2012-03-21 | 广州市云通磁电有限公司 | Manufacturing method of lithium iron phosphate-cobalt acid lithium composite anode plate of lithium ion battery |
| KR20130104088A (en) * | 2012-03-12 | 2013-09-25 | 삼성에스디아이 주식회사 | Electrode assembly and lithium recheabable battery comprising the same |
| WO2014189329A1 (en) * | 2013-05-23 | 2014-11-27 | 주식회사 엘지화학 | Lithium secondary battery comprising multilayered active material layer |
| JP6469450B2 (en) * | 2014-02-27 | 2019-02-13 | パナソニック株式会社 | Positive electrode for non-aqueous electrolyte secondary battery and non-aqueous electrolyte secondary battery |
| KR102062689B1 (en) * | 2016-11-23 | 2020-01-06 | 주식회사 엘지화학 | Positive electrode for secondary battery and lithium secondary battery comprising the same |
| CN107482166A (en) * | 2017-07-03 | 2017-12-15 | 深圳市比克动力电池有限公司 | A kind of lithium ion battery |
-
2018
- 2018-09-06 CN CN201811038433.0A patent/CN109119619B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102891299A (en) * | 2012-09-12 | 2013-01-23 | 黎军 | High-rate lithium ion battery cathode material and preparation method and application thereof |
| CN106450199A (en) * | 2016-10-24 | 2017-02-22 | 东莞市联洲知识产权运营管理有限公司 | Preparation method of safe and environment-friendly high-rate lithium-ion battery |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109119619A (en) | 2019-01-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109119619B (en) | A kind of preparation method of the lithium ion cell positive of high rate capability | |
| Li et al. | Sphere-like SnO2/TiO2 composites as high-performance anodes for lithium ion batteries | |
| CN104157854B (en) | A kind of preparation method of Graphene composite lithium ion cell tertiary cathode material | |
| WO2017005078A1 (en) | Ternary material coated with three-dimensional network structure of coupled carbon nanotube-graphene composite and manufacturing method thereof | |
| CN108933242B (en) | Preparation method of lithium ion battery mixed anode | |
| CN105118972B (en) | Metal hydroxide coated carbon and sulfur lithium-sulfur battery positive electrode material, and preparation method and application thereof | |
| CN103050683B (en) | Polyphase manganese base solid solution composite cathode material and preparation method thereof | |
| CN107785541A (en) | A kind of Silicon-carbon composite material for lithium ion battery and preparation method thereof | |
| CN107845802B (en) | A kind of conducting polymer for lithium battery coats cobalt acid lithium and preparation method thereof | |
| CN107204461B (en) | A kind of anode material for lithium-ion batteries and preparation method thereof | |
| CN103094558A (en) | Zinc-ferrite-based nanometer composite as well as preparation method and application thereof | |
| CN101714627A (en) | Carbon nanotube/lithium iron phosphate composite positive electrode material and in situ preparation method thereof | |
| CN106558729B (en) | A kind of lithium ion battery of graphene as anode sizing agent conductive agent | |
| CN103904335A (en) | Lithium ion battery negative material structure and preparation method thereof | |
| CN109659519B (en) | TiO2Preparation method of nanofiber-coated lithium ion battery ternary cathode material and product | |
| CN106356502A (en) | High-rate-performance lithium iron phosphate battery positive electrode plate and preparation method thereof | |
| CN110233284A (en) | A kind of low form high-energy density long circulating ferric phosphate lithium cell | |
| CN107887594A (en) | A kind of compound lithium-rich manganese-based anode material and preparation method for lithium ion battery | |
| CN109148860A (en) | A kind of nickelic positive electrode and preparation method thereof and lithium ion battery | |
| CN110492097A (en) | A kind of NCM ternary composite cathode material and its preparation and application | |
| CN112201783A (en) | Positive pole piece for lithium ion battery with high cost performance and long cycle life | |
| CN112331839B (en) | MXene-doped and surface-coated modified lithium ion battery positive electrode material and preparation method thereof | |
| CN101289576B (en) | Composite material of conducting high polymers/alloy for nickel-hydrogen battery and preparation thereof | |
| CN110335996A (en) | A kind of high capacity lithium ion cells cathode and its application | |
| CN110010873B (en) | Preparation method of mixed anode slurry |
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 | ||
| CB03 | Change of inventor or designer information |
Inventor after: Zeng Jinhui Inventor after: Fang Zhiyi Inventor after: Li Zhuang Inventor before: Li Zhuang |
|
| CB03 | Change of inventor or designer information | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20191022 Address after: 344000 Jiangxi province Fuzhou City Jinchao Economic Development Zone, hi tech Industrial Park Applicant after: Jiangxi Dibico Co., Ltd. Address before: 215000 No. 288 Ganjiang West Road, Gusu District, Suzhou City, Jiangsu Province Applicant before: Li Zhuang |
|
| TA01 | Transfer of patent application right | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: A preparation method of lithium ion battery cathode with high rate performance Effective date of registration: 20201217 Granted publication date: 20191119 Pledgee: Fuzhou hi tech Zone Industry and technology Financing Guarantee Co., Ltd Pledgor: Jiangxi DBK Corporation Co.,Ltd. Registration number: Y2020360000110 |
|
| PE01 | Entry into force of the registration of the contract for pledge of patent right |