CN110518223A - A kind of coating aluminium foil and preparation method thereof - Google Patents
A kind of coating aluminium foil and preparation method thereof Download PDFInfo
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- CN110518223A CN110518223A CN201910840497.0A CN201910840497A CN110518223A CN 110518223 A CN110518223 A CN 110518223A CN 201910840497 A CN201910840497 A CN 201910840497A CN 110518223 A CN110518223 A CN 110518223A
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- aluminium foil
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
- H01M4/364—Composites as mixtures
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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- 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
Abstract
The present invention relates to electrochemical field, a kind of coating aluminium foil and preparation method thereof is disclosed.The coating aluminium foil includes aluminium foil and coated on the rich lithium coating on aluminium foil surface, and the richness lithium coating contains conductive agent, binder and ferrous acid lithium material, wherein the ferrous acid lithium material includes Li5FeO4With the amorphous carbon layer for being coated on its surface, and content of the amorphous carbon layer in ferrous acid lithium material be 0.5-15 weight %.Coating aluminium foil prepared by the present invention can reduce battery existing reversible capacity loss during first charge-discharge, and then improve battery energy density.
Description
Technical field
The present invention relates to electrochemical fields, and in particular to a kind of coating aluminium foil and preparation method thereof.
Background technique
Along with the environmental pollution and energy crisis of global range, various new energy technologies cause the pass of people
Note.Wherein, lithium ion battery is due to having the features such as high-energy density, high working voltage, long circulation life, small environment pollution,
As one of the secondary cell being most widely used at present.With the continuous development of battery technology and going out for national relevant policies
Platform, research staff have increasingly higher demands for the energy density of lithium ion secondary battery.
However, lithium ion battery during first charge-discharge there is active material configuration collapsing, active material falls off
And the reaction such as formation of solid electrolyte interface film, so that the reversible capacity of lithium ion battery and first charge discharge efficiency decline, lead
Cause battery energy density decline.
Summary of the invention
The purpose of the invention is to overcome lithium ion battery existing in the prior art to make during first charge-discharge
At reversible capacity loss and first charge discharge efficiency decline, and then caused battery energy density decline the problem of, provide one kind
Coat aluminium foil and preparation method thereof.
To achieve the goals above, one aspect of the present invention provides a kind of coating aluminium foil, and the coating aluminium foil includes aluminium foil
And coated on the rich lithium coating on aluminium foil surface, the richness lithium coating contains conductive agent, binder and ferrous acid lithium material,
In, the ferrous acid lithium material includes Li5FeO4With the amorphous carbon layer for being coated on its surface, and the amorphous carbon layer is in ferrous acid
Content in lithium material is 0.5-15 weight %.
Preferably, the rich lithium coating with a thickness of 0.5-100 μm.
Preferably, in the rich lithium coating, with the total amount of the ferrous acid lithium material, the conductive agent and the binder
For 100 weight % meter, the content of the ferrous acid lithium material is 50-95 weight %, and the content of the conductive agent is 1-45 weight %,
The content of the binder is 1-15 weight %.
Preferably, the conductive agent is one in carbon black, electrically conductive graphite, carbon nanotube, Ketjen black, acetylene black and graphene
Kind is a variety of；
Preferably, the binder is polyvinylidene fluoride.
Another aspect of the present invention provides the preparation method of above-mentioned coating aluminium foil, the described method comprises the following steps:
(1) by binder and part dispersant, adhesive gelatin is obtained；
(2) adhesive gelatin for obtaining step (1) and ferrous acid lithium material, conductive agent and remainder dispersant,
Dispersion, obtains rich lithium slurry；
(3) the rich lithium slurry is coated on the surface of aluminium foil, it is dry.
Preferably, in the rich lithium slurry, the total concentration of the binder, the conductive agent and the ferrous acid lithium material
For 25-50 weight %.
Preferably, in step (1), the concentration of binder is 3-8 weight % in the adhesive gelatin.
Preferably, in step (1) and (2), the dispersing agent is N-Methyl pyrrolidone.
Preferably, the method also includes preparing the ferrous acid lithium material according to following process:
(a) source of iron, lithium source, carbon source and deionized water are mixed, obtains mixed liquor；
(b) mixed liquor for obtaining step (a) is ground so that in mixed liquor solid particle granularity be 0.4 μm with
Under；
(c) mixed liquor after grinding is spray-dried, obtains ferrous acid lithium presoma；
(d) the ferrous acid lithium presoma is sintered, crushed, obtain ferrous acid lithium material；
Wherein, the dosage of the carbon source makes the content of material with carbon-coated surface layer in prepared ferrous acid lithium material be 0.5-15
Weight %；
The molar ratio of Li/Fe is (5-25) in the lithium source and the source of iron: 1；
Preferably, the lithium source and the molar ratio of Li/Fe in the source of iron are (6-12): 1；
Preferably, in step (a), the source of iron is Fe2O3、Fe3O4, FeOOH, in ferric nitrate and ironic citrate extremely
Few one kind；
Preferably, in step (a), the lithium source is Li2CO3And/or LiOHH2O；
Preferably, in step (a), the carbon source be phenolic resin, polyvinyl alcohol, citric acid, stearic acid, glucose,
At least one of sucrose, polyvinyl chloride and polyethylene glycol；
Preferably, in step (c), the spray drying condition includes: that spray inlet temperature is 110-180 DEG C, preferably
It is 120-160 DEG C；Spray outlet temperature is 70-120 DEG C, preferably 80-100 DEG C；
Preferably, in step (d), the sintering condition includes: that temperature is 650-1000 DEG C, preferably 800-900 DEG C；
Time is 3-72h, preferably 24-48h.
The coating aluminium foil containing rich lithium coating being prepared through the above technical solution, is reducing positive electrode and aluminium foil
Between contact resistance while, can also reduce battery during first charge-discharge reversible capacity loss and first charge discharge efficiency under
Drop, and then improve battery energy density.
Detailed description of the invention
Fig. 1 is the XRD diagram of ferrous acid lithium material made from embodiment 1.
Specific embodiment
Below in conjunction with attached drawing, detailed description of the preferred embodiments.It should be understood that this place is retouched
The specific embodiment stated is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
One aspect of the present invention provides a kind of coating aluminium foil, and the coating aluminium foil includes aluminium foil and is coated on aluminium foil surface
On rich lithium coating, it is described richness lithium coating contain conductive agent, binder and ferrous acid lithium material, wherein the ferrous acid lithium material packet
Include Li5FeO4With the amorphous carbon layer for being coated on its surface, and content of the amorphous carbon layer in ferrous acid lithium material be 0.5-
15 weight %.
In the present invention, the aluminium foil is the conventional selection of this field, such as can be 5-30 μm of thickness of aluminium foil.
In the present invention, the coating method is well known to those skilled in the art, such as can be spray gun spraying, coating
Machine coating, electrostatic spinning or scraper blade coating etc..
In the present invention, the thickness of rich lithium coating is not particularly limited, in a preferred embodiment, the richness lithium
Coating with a thickness of 0.5-100 μm, specifically, for example can be 0.5 μm, 5 μm, 10 μm, 15 μm, 20 μm, 30 μm, 40 μm, 50 μ
M, 60 μm, 70 μm, 80 μm, 90 μm or 100 μm, preferably 5-20 μm.
In the present invention, in the rich lithium coating, with the ferrous acid lithium material, the conductive agent and the binder
Total amount is 100 weight % meter, and the content of the ferrous acid lithium material can be 50-95 weight %, and the content of the conductive agent can be with
For 1-45 weight %, the content of the binder can be 1-15 weight %.
In the preferred case, in the rich lithium coating, with the ferrous acid lithium material, the conductive agent and the binder
Total amount be 100 weight % meter, the content of the ferrous acid lithium material is 65-85 weight %, and the content of the conductive agent is 5-25
Weight %, the content of the binder are 4-13 weight %.
In the present invention, the conductive agent can be the conventional selection of this field, in a preferred embodiment, described to lead
Electric agent is one of carbon black (Super-P), electrically conductive graphite (Ks-6), carbon nanotube, Ketjen black, acetylene black and graphene or more
Kind, preferably carbon black (Super-P) and/or electrically conductive graphite (Ks-6).
In the present invention, the binder can be the conventional selection of this field, in a preferred embodiment, described viscous
Knot agent is polyvinylidene fluoride (PVDF).
Another aspect of the present invention provides the preparation method of above-mentioned coating aluminium foil, the described method comprises the following steps:
(1) by binder and part dispersant, adhesive gelatin is obtained；
(2) adhesive gelatin for obtaining step (1) and ferrous acid lithium material, conductive agent and remainder dispersant,
Dispersion, obtains rich lithium slurry；
(3) the rich lithium slurry is coated on the surface of aluminium foil, it is dry.
Method according to the present invention, it is the binder, described in situations where it is preferred, in the rich lithium slurry
The total concentration of conductive agent and the ferrous acid lithium material is 25-50 weight %, specifically, for example can for 25%, 28%, 30%,
33%, 36%, 38%, 40%, 43%, 46%, 49% or 50%, preferably 28-40%.
Binder and part dispersant are that adhesive property is stronger in order to obtain by method according to the present invention
Adhesive gelatin, the concentration of binder is not particularly limited in the adhesive gelatin, in a preferred embodiment, in step
Suddenly in (1), the concentration of binder is 3-8 weight % in the adhesive gelatin, specifically, for example can be 3 weight %, 4 weights
Measure %, 5 weight %, 6 weight %, 7 weight % or 8 weight %, preferably 4-6 weight %.
Method according to the present invention, in step (2), the dispersion process can be stirred in ball grinder or stainless steel
It is carried out in cylinder.Fully dispersed rich lithium slurry in order to obtain can disperse the ferrous acid lithium material, conductive agent and remainder
Agent is added in batches according to the actual situation.
Method according to the present invention, the dispersing agent can be the conventional selection of this field, in preferred embodiment party
In formula, in step (1) and (2), the dispersing agent is N-Methyl pyrrolidone (NMP).
Method according to the present invention, in step (3), the drying process can be in convection oven and/or vacuum
It is carried out in drying box.
Method according to the present invention, the method also includes preparing the ferrous acid lithium material according to following process:
(a) source of iron, lithium source, carbon source and deionized water are mixed, obtains mixed liquor；
(b) mixed liquor for obtaining step (a) is ground so that in mixed liquor solid particle granularity be 0.4 μm with
Under；
(c) mixed liquor after grinding is spray-dried, obtains ferrous acid lithium presoma；
(d) the ferrous acid lithium presoma is sintered, crushed, obtain ferrous acid lithium material；
Wherein, the dosage of the carbon source allows the content of material with carbon-coated surface layer in prepared ferrous acid lithium material to be
0.5-15 weight %, specifically, for example can be 0.5 weight %, 1 weight %, 3 weight %, 5 weight %, 7 weight %, 9 weights
Measure %, 11 weight %, 13 weight % and 15 weight %.
The molar ratio of Li/Fe can be (5-25) in method according to the present invention, the lithium source and the source of iron: 1,
Specifically, can be for example 5:1,6:1,9:1,12:1,15:1,18:1,21:1,24:1 or 25:1, in preferred embodiment
In, the molar ratio of Li/Fe is (6-12) in the lithium source and the source of iron: 1.
Method according to the present invention, in step (a), the source of iron can be the conventional selection of this field, excellent
In the embodiment of choosing, the source of iron is Fe2O3、Fe3O4, FeOOH, at least one of ferric nitrate and ironic citrate, preferably
Fe2O3。
Method according to the present invention, in step (a), the lithium source can be the conventional selection of this field, excellent
In the embodiment of choosing, the lithium source is Li2CO3And/or LiOHH2O。
Method according to the present invention, in step (a), the carbon source can be the conventional selection of this field, excellent
In the embodiment of choosing, the carbon source is phenolic resin, polyvinyl alcohol, citric acid, stearic acid, glucose, sucrose, polyvinyl chloride
At least one of with polyethylene glycol, preferably glucose, sucrose and polyethylene glycol.
Method according to the present invention, in step (c), the mixed liquor after grinding need to carry out spray drying treatment,
The spray drying treatment condition is not particularly limited.In a preferred embodiment, the spray inlet temperature is 110-180
DEG C, preferably 120-160 DEG C, further preferably 130-140 DEG C；The spray outlet temperature is 70-120 DEG C, preferably 80-
110 DEG C, further preferably 85-95 DEG C.
In the present invention, in step (d), the sintering method is well known to those skilled in the art.Preferred real
It applies in mode, the sintering is in N2It protects under atmosphere, is heated up in van-type furnace with 1-6 DEG C/min, the sintering temperature
It is 650-1000 DEG C, preferably 700-950 DEG C, further preferably 850-900 DEG C；The sintering time is 3-72h, preferably
10-60h, further preferably 24-48h.
In the present invention, first charge discharge efficiency=first discharge specific capacity/initial charge specific capacity × 100%.In full electricity
In the experiment of pond, first charge-discharge specific capacity and first charge discharge efficiency are higher, show that prepared coating aluminium foil more can be used for solving head
The problem of loss of battery reversible capacity caused by secondary charge and discharge and first charge discharge efficiency decline.
In the present invention, the ferrous acid lithium material is single crystal form, without miscellaneous phase, and surface is also wrapped on amorphous carbon layer,
It makes it have preferable electrical property and preferable capacity plays, and contain five parts of lithiums in every part of ferrous acid lithium material, be introduced into
To aluminium foil surface, the coating aluminium foil containing rich lithium coating being prepared is reducing contact resistance between positive electrode and aluminium foil
While, the reversible capacity loss and first charge discharge efficiency decline of battery, Jin Erti can also be reduced during first charge-discharge
High battery energy density.
The present invention will be described in detail by way of examples below, but scope of protection of the present invention is not limited thereto.
Embodiment 1
(1) prepared by ferrous acid lithium material
By 1548g LiOHH2O、500g Fe2O3, 105g glucose and deionized water mixing, be added in grinder into
Row grinding, so that the granularity of solid particle is 150nm hereinafter, being spray-dried later to mixed liquor in mixed liquor, wherein spray
Mist inlet temperature is 135 DEG C, and outlet temperature is 90 DEG C, obtains Li5FeO4Presoma, by the Li5FeO4Presoma is placed in saggar
In, it places into van-type furnace, in N2Protect atmosphere under, be warming up to 850 DEG C with 2 DEG C/min and be sintered, sintering time be for 24 hours,
It is crushed to obtain ferrous acid lithium material later.
(2) coating aluminium foil preparation
1.5g PVDF and 28.5g NMP are mixed and dispersed, adhesive gelatin is obtained, by adhesive gelatin and 12g ferrous acid lithium
Material, 1.5g Super-P are added in ball grinder, and 1.5g NMP is added dropwise, and are added agate ball ball milling dispersion 20min, are obtained richness
The rich lithium slurry is coated on a surface of aluminium foil on automatic coating device using coating device, is distinguished later by lithium slurry
It is dried in 80 DEG C of convection ovens and 125 DEG C of vacuum ovens, obtains target coat aluminium foil, wherein the aluminium foil table
Face richness lithium coating with a thickness of 20 μm.
Embodiment 2
(1) prepared by ferrous acid lithium material
By 924g Li2CO3、196g Fe2O3, 200g sucrose and deionized water mixing, be added in grinder and ground
Mill, so that the granularity of solid particle is 200nm hereinafter, being spray-dried later to mixed liquor in mixed liquor, wherein it is spraying into
Mouth temperature is 140 DEG C, and outlet temperature is 95 DEG C, obtains Li5FeO4Presoma, by the Li5FeO4Presoma is placed in saggar,
It places into van-type furnace, in N2It protects under atmosphere, is warming up to 900 DEG C with 5 DEG C/min and is sintered, sintering time 48h, later
It is crushed to obtain ferrous acid lithium material.
(2) coating aluminium foil preparation
120g PVDF and 1880g NMP are mixed and dispersed, adhesive gelatin is obtained, by adhesive gelatin and 1000g
Li5FeO4And 90g Super-P is added in 10L stainless steel a mixing bowl, disperses 10min, adds 1000g Li5FeO4And
330g NMP continues to disperse 60min, and scraper after uncapping adds 150g NMP glue, so observes pulp-like afterwards in triplicate
State adds the viscosity of 180gKs-6 and 950g NMP adjustment slurry later, obtains rich lithium slurry by defoaming sieving.By rich lithium
Slurry is added in trough of coating machine, adjusts comma knife up degree, rich lithium slurry is transferred on aluminium foil by steel rod, through 120 DEG C of baking ovens
Single side coating aluminium foil is obtained after drying.Wherein, the aluminium foil surface richness lithium coating with a thickness of 15 μm.
Embodiment 3
(1) prepared by ferrous acid lithium material
By 2000g LiOHH2O、317g Fe2O3, 150g polyethylene glycol and deionized water mixing, be added in grinder
It is ground, so that the granularity of solid particle is 300nm hereinafter, being spray-dried later to mixed liquor in mixed liquor, wherein
Spray inlet temperature is 130 DEG C, and outlet temperature is 85 DEG C, obtains Li5FeO4Presoma, by the Li5FeO4Presoma is placed in casket
In alms bowl, place into van-type furnace, in N2It protects under atmosphere, is warming up to 870 DEG C with 3 DEG C/min and is sintered, sintering time is
30h is crushed to obtain ferrous acid lithium material later.
(2) coating aluminium foil preparation
150g PVDF and 3700g NMP are mixed and dispersed, adhesive gelatin is obtained, by adhesive gelatin and 1000g
Li5FeO4And 150g Super-P is added in 10L stainless steel a mixing bowl, disperses 10min, adds 500g Li5FeO4And
The anhydrous NMP of 330g continues to disperse 60min, and scraper after uncapping is added 200g NMP glue, so observes pulp-like afterwards in triplicate
State adds the viscosity of 150gKS-6 and 420g NMP adjustment slurry later, obtains rich lithium slurry by defoaming sieving.By rich lithium
Slurry is added in trough of coating machine, adjusts comma knife up degree, rich lithium slurry is transferred on aluminium foil by steel rod, through 120 DEG C of baking ovens
Single side coating aluminium foil is obtained after drying.Wherein, the aluminium foil surface richness lithium coating with a thickness of 10 μm.
Comparative example 1
(1) prepared by ferrous acid lithium material
In addition to not having process of lapping, remaining process is the same as embodiment 1.
(2) coating aluminium foil preparation
With 1 preparation process of embodiment.
Comparative example 2
(1) prepared by ferrous acid lithium material
In addition to glucose is not added, remaining process is the same as embodiment 1.
(2) coating aluminium foil preparation
With 1 preparation process of embodiment.
Comparative example 3
Preparation process without ferrous acid lithium material, directly as a comparison case with the aluminium foil of no coating any material.
Test case 1
Ferrous acid lithium material made from embodiment 1 is measured using X-ray diffractometer, as a result as shown in Figure 1.
As shown in Figure 1, the peak type of the diffraction maximum of embodiment matches with PDF card (PCPDF:24-0623), out peak position
It is consistent, no dephasign peak, shows the Li obtained5FeO4Material is single crystal form, without miscellaneous phase.
Test case 2
Using aluminium foil described in embodiment 1-3 and comparative example 1-3 as plus plate current-collecting body, using 811 material of ternary as just
Pole material prepares anode sizing agent according to positive electrode, conductive agent (Super-P), bonding agent (PVDF) mass ratio 90:5:5, will make
The anode sizing agent got ready is respectively coated on aluminium foil, obtains anode pole piece after drying, roll-in, punching；Using graphite material conduct
Negative electrode material, according to negative electrode material, conductive agent (Super-P), thickener (CMC), bonding agent (SBR) mass ratio 94:2:1.5:
2.5 prepare negative electrode slurry, and the negative electrode slurry prepared is coated on copper foil, obtain cathode pole piece after drying, roll-in, punching；
The assembly of 2032 battery of button is carried out in glove box, electrolyte is the LiPF of 1.2mol/L6, using ethylene carbonate: carbonic acid first
Ethyl ester=3:7 (volume ratio) is used as solvent, and diaphragm is Celgard polypropylene screen.
Above-mentioned 6 kinds of lithium ion batteries are taken to carry out volume test on new prestige tester respectively, charging is 4.3V by voltage,
Discharge cut-off voltage is 3.0V, charge-discharge magnification 0.1C, and test result is as shown in table 1.
Table 1
By 1 test result of table it is found that coating aluminium foil is prepared using technical solutions according to the invention, using its as
The plus plate current-collecting body of lithium ion battery has preferable charging and discharging capacity, i.e., imitates for the first time in charging when voltage is 4.3V
Rate is improved.It is indicated above that the coating aluminium foil can be used for solving lithium ion battery existing for the first charge-discharge process
The problem of reversible capacity loss and first charge discharge efficiency decline, and then battery energy density can be improved.
The preferred embodiment of the present invention has been described above in detail, and still, the present invention is not limited thereto.In skill of the invention
In art conception range, can with various simple variants of the technical solution of the present invention are made, including each technical characteristic with it is any its
Its suitable method is combined, and it should also be regarded as the disclosure of the present invention for these simple variants and combination, is belonged to
Protection scope of the present invention.
Claims (10)
1. a kind of coating aluminium foil, which is characterized in that the coating aluminium foil includes aluminium foil and coated on the rich lithium on aluminium foil surface
Coating, the richness lithium coating contain conductive agent, binder and ferrous acid lithium material, wherein the ferrous acid lithium material includes Li5FeO4
With the amorphous carbon layer for being coated on its surface, and content of the amorphous carbon layer in ferrous acid lithium material be 0.5-15 weight
Measure %.
2. coating aluminium foil according to claim 1, which is characterized in that it is described richness lithium coating with a thickness of 0.5-100 μm.
3. coating aluminium foil according to claim 1, which is characterized in that in the rich lithium coating, with the ferrous acid lithium material
The total amount of material, the conductive agent and the binder is 100 weight % meter, and the content of the ferrous acid lithium material is 50-95 weight
% is measured, the content of the conductive agent is 1-45 weight %, and the content of the binder is 1-15 weight %.
4. coating aluminium foil according to claim 1 or 3, which is characterized in that the conductive agent is carbon black, electrically conductive graphite, carbon
One of nanotube, Ketjen black, acetylene black and graphene are a variety of；
Preferably, the binder is polyvinylidene fluoride.
5. a kind of preparation method of the coating aluminium foil as described in any one of claim 1-4, which is characterized in that the method
The following steps are included:
(1) by binder and part dispersant, adhesive gelatin is obtained；
(2) adhesive gelatin for obtaining step (1) and ferrous acid lithium material, conductive agent and remainder dispersant, dispersion,
Obtain rich lithium slurry；
(3) the rich lithium slurry is coated on the surface of aluminium foil, it is dry.
6. according to the method described in claim 5, it is characterized in that, in the rich lithium slurry, the binder, the conduction
The total concentration of agent and the ferrous acid lithium material is 25-50 weight %.
7. according to the method described in claim 5, it is characterized in that, in step (1), binder in the adhesive gelatin
Concentration is 3-8 weight %.
8. the method according to claim 5 or 7, which is characterized in that in step (1) and (2), the dispersing agent is N- first
Base pyrrolidones.
9. method according to claim 5 or 6, which is characterized in that the method also includes preparing institute according to following process
State ferrous acid lithium material:
(a) source of iron, lithium source, carbon source and deionized water are mixed, obtains mixed liquor；
(b) mixed liquor for obtaining step (a) is ground, so that the granularity of solid particle is 0.4 μm or less in mixed liquor；
(c) mixed liquor after grinding is spray-dried, obtains ferrous acid lithium presoma；
(d) the ferrous acid lithium presoma is sintered, crushed, obtain ferrous acid lithium material；
Wherein, the dosage of the carbon source makes the content of material with carbon-coated surface layer in prepared ferrous acid lithium material for 0.5-15 weight
Measure %；
The molar ratio of Li/Fe is (5-25) in the lithium source and the source of iron: 1.
10. according to the method described in claim 9, it is characterized in that, the lithium source and the molar ratio of Li/Fe in the source of iron are
(6-12): 1；
Preferably, in step (a), the source of iron is Fe2O3、Fe3O4, FeOOH, at least one in ferric nitrate and ironic citrate
Kind；
Preferably, in step (a), the lithium source is Li2CO3And/or LiOHH2O；
Preferably, in step (a), the carbon source be phenolic resin, polyvinyl alcohol, citric acid, stearic acid, glucose, sucrose,
At least one of polyvinyl chloride and polyethylene glycol；
Preferably, in step (c), the spray drying condition includes: that spray inlet temperature is 110-180 DEG C, preferably
120-160℃；Spray outlet temperature is 70-120 DEG C, preferably 80-100 DEG C；
Preferably, in step (d), the sintering condition includes: that temperature is 650-1000 DEG C, preferably 800-900 DEG C；Time
For 3-72h, preferably 24-48h.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106025184A (en) * | 2016-05-27 | 2016-10-12 | 佛山市金银河智能装备股份有限公司 | Production process for lithium battery slurry |
| CN108878849A (en) * | 2018-07-04 | 2018-11-23 | 江西中汽瑞华新能源科技有限公司 | The synthesis technology of rich oxidate for lithium and lithium ion battery containing the richness oxidate for lithium |
| CN109686947A (en) * | 2018-12-25 | 2019-04-26 | 遵化市清吉电池科技有限公司 | With the lithium battery aluminium foil and its positive plate of lithium battery of mending lithium coating and lithium battery |
| CN109755448A (en) * | 2018-12-28 | 2019-05-14 | 北京中能东道绿驰科技有限公司 | A kind of lithium battery diaphragm and preparation method thereof with benefit lithium coating |
-
2019
- 2019-09-06 CN CN201910840497.0A patent/CN110518223A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106025184A (en) * | 2016-05-27 | 2016-10-12 | 佛山市金银河智能装备股份有限公司 | Production process for lithium battery slurry |
| CN108878849A (en) * | 2018-07-04 | 2018-11-23 | 江西中汽瑞华新能源科技有限公司 | The synthesis technology of rich oxidate for lithium and lithium ion battery containing the richness oxidate for lithium |
| CN109686947A (en) * | 2018-12-25 | 2019-04-26 | 遵化市清吉电池科技有限公司 | With the lithium battery aluminium foil and its positive plate of lithium battery of mending lithium coating and lithium battery |
| CN109755448A (en) * | 2018-12-28 | 2019-05-14 | 北京中能东道绿驰科技有限公司 | A kind of lithium battery diaphragm and preparation method thereof with benefit lithium coating |
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