CN109449408A - A kind of ferric flouride-Asia titanium oxide composite positive pole and its preparation method and application - Google Patents
A kind of ferric flouride-Asia titanium oxide composite positive pole and its preparation method and application Download PDFInfo
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Abstract
The present invention relates to a kind of ferric flouride-Asia titanium oxide composite positive pole and its preparation method and application, the composite positive pole is spherical structure, including kernel and clad, and the kernel is ferric flouride and sub- titanium oxide, and the clad is carbon material.The present invention makes sub- titanium oxide and carbon material jointly granule modified to ferric flouride in the way of spray drying, and formation body phase inside point contact type is compound with external face contact type, has obtained the multi-layer spherical structure of kernel and clad composition.Under modified material and the collective effect of special construction, ferric flouride-Asia titanium oxide composite positive pole that the present invention obtains still is able to maintain preferable cyclical stability and capacity retention ratio at higher voltages, has a good application prospect.
Description
Technical field
The present invention relates to anode material for lithium-ion batteries technical fields, and in particular to a kind of ferric flouride-Asia titanium oxide is compound
Positive electrode and its preparation method and application.
Background technique
With greatly developing for new-energy automobile, lithium ion battery industry comes into Rapid development stage.Influence lithium from
The critical material of sub- battery performance mainly has positive electrode, negative electrode material, electrolyte etc..Wherein, positive electrode is to limit at present
The principal element of battery performance, while being also the principal element for accounting for lithium ion battery higher cost, close to 40%.Positive electrode current material
Material mainly has cobalt acid lithium, nickle cobalt lithium manganate or nickel cobalt lithium aluminate ternary material, LiMn2O4, LiFePO4 etc., but with new energy
The fast development of source automobile is gradually increased positive electrode demand, and to be also faced with resource limited for the elements such as nickel, cobalt, and price is high
Your the problems such as.
Ferric flouride as emerging conversion hysteria anode material for lithium-ion batteries, can use whole oxidation state of ferro element with
Chemical conversioning reaction occurs for lithium ion to store energy, with the transfer of three electronics, has very high theoretical specific capacity.But by
Big in metal fluoride band gap, electric conductivity is poor, it is therefore desirable to further modified.
CN103855389A discloses a kind of borontrifluoride iron/carbon composite and its preparation method and application, utilizes carbon pair
Ferric flouride is modified, which includes the borontrifluoride iron of 50~90wt% and the carbon material of 10~50wt%.
CN105958040A provides a kind of borontrifluoride iron composite material, utilizes multi-component conduction of the doped and compounded on borontrifluoride iron
Polymer is modified borontrifluoride iron, and conducting polymer is two kinds or more in polyaniline, polyurethane, polypyrrole and polythiophene
Kind.CN107591524A discloses a kind of preparation method of graphene-ferric fluoride composite cathode material, and fluorination iron material is carried out
Cobalt doped it is modified again with the good silicon doped graphene Material cladding of electric conductivity and stability.CN106025182A is public
A kind of titanium chromium doping ferric flouride-carbon nano composite anode material and preparation method thereof has been opened, shape after titanium ion and chromium ion is adulterated
It coats to obtain at ferric flouride presoma, then through carbon containing conductive material.CN106099074A discloses a kind of titanium doped ferric flouride
The preparation method of positive electrode, the material general formula are Fe1-xTixF3·0.33H2O/C, 0.01≤x≤0.50.CN107146881A
It discloses a kind of Modified Nickel lithium manganate cathode composite material, including nickel ion doped particle, is coated on the nickel ion doped particle table
The fluorination iron layer in face and the graphene layer for being coated on the fluorination iron layer.
Except through doping mode the performance of ferric flouride is improved except, structure be also influence its performance it is important
Factor.Therefore how modification further to be doped to ferric flouride, and designs suitable structure, to solve to be fluorinated in the prior art
The problem of iron poorly conductive, while its being made to obtain superior performance, the direction that the person that becomes current research makes great efforts.
Summary of the invention
In view of problems of the prior art, the purpose of the present invention is to provide a kind of ferric flouride-Asia titanium oxide is compound
Positive electrode and its preparation method and application is jointly modified ferric flouride using sub- titanium oxide and carbon material, and constructs
Multi-layer spherical structure, can promote the electric conductivity and structural stability of material entirety, so improve material cycle performance and
High rate performance has a good application prospect.
To achieve this purpose, the present invention adopts the following technical scheme:
In a first aspect, the present invention provides a kind of ferric flouride-Asia titanium oxide composite positive pole, the composite positive pole
For spherical structure, including kernel and clad, the kernel is ferric flouride and sub- titanium oxide, and the clad is carbon material.
The present invention chooses sub- titanium oxide and carbon material is jointly modified ferric flouride.Wherein, sub- titanium oxide (T4O7) have
The conductivity of superelevation, and the advantages that good electrochemical stability and corrosion resistance；Carbon material electric conductivity is strong, specific surface area
Greatly, have certain flexibility, can padded coaming volume change.Make sub- titanium oxide and carbon material total in the way of spray drying
With granule modified to ferric flouride, the compound of point contact type and external face contact type inside body phase is formed, kernel and cladding have been obtained
The multi-layer spherical structure that layer is constituted.Under modified material and the collective effect of special construction, ferric flouride-Asia that the present invention obtains
Titanium oxide composite positive pole can be improved the thermal stability of battery material, cycle performance and forthright again.
According to the present invention, based on mass percentage, the content of composite positive pole Central Asia titanium oxide is 1-15%,
Such as can be specific point value between 1%, 3%, 5%, 8%, 10%, 13% or 15% and above-mentioned numerical value, as space is limited
And for concise consideration, the present invention no longer exclusive list.
According to the present invention, based on mass percentage, the content of carbon material is 1-40%, example in the composite positive pole
It such as can be specific between 1%, 5%, 10%, 15%, 20%, 25%, 30%, 35% or 40% and above-mentioned numerical value
Value, as space is limited and for concise consideration, the present invention no longer exclusive list.
Based on mass percentage, ferric flouride, sub- the sum of titanium oxide and carbon material in composite positive pole of the present invention
It is 100%.
According to the present invention, the partial size of the composite positive pole be 1-20 μm, such as can be 1 μm, 3 μm, 5 μm, 8 μm,
Specific point value between 10 μm, 13 μm, 15 μm, 18 μm or 20 μm and above-mentioned numerical value is examined as space is limited and for concise
Consider, the present invention no longer exclusive list.
According to the present invention, ferric flouride and sub- titanium oxide exist in the form of compound and independent particle in the kernel,
The independent particle refers to the fluorination iron particle only contacted respectively with carbon material and sub- titan oxide particles.
According to the present invention, the structural formula of the ferric flouride and sub- titanium oxide compound is FeF3/T4O7, the compound
Partial size is 0.9-9 μm, such as can be 0.9 μm, 1 μm, 2 μm, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm or 9 μm and above-mentioned number
Specific point value between value, as space is limited and for concise consideration, the present invention no longer exclusive list.
According to the present invention, it is described fluorination iron particle partial size be 0.5-5 μm, such as can be 0.5 μm, 1 μm, 2 μm, 3 μm,
Specific point value between 4 μm or 5 μm and above-mentioned numerical value, as space is limited and for concise consideration, the no longer exhaustive column of the present invention
It lifts.
According to the present invention, the partial size of the sub- titan oxide particles is 0.5-5 μm, such as can be 0.5 μm, 1 μm, 2 μm, 3 μ
M, the specific point value between 4 μm or 5 μm and above-mentioned numerical value, as space is limited and for concise consideration, the present invention is no longer exhaustive
It enumerates.
Second aspect, the present invention provides the preparation method of composite positive pole as described in relation to the first aspect, the methods
The following steps are included:
(1) it disperses ferric flouride and sub- titanium oxide in solvent by formula ratio, carbon source is then added, obtains composite solution；
(2) composite solution that step (1) obtains is spray-dried, obtains the composite positive pole.
According to the present invention, step (1) solvent is water, ethyl alcohol, acetone, propyl alcohol, isopropanol, isobutanol, methanol, positive fourth
In alcohol, ethylene glycol or chloroform any one or at least two combination, such as can be water, ethyl alcohol, acetone, propyl alcohol, isopropyl
Any one in alcohol, isobutanol, methanol, n-butanol, ethylene glycol or chloroform, typical but non-limiting combination are as follows: water and second
Alcohol, acetone and propyl alcohol, isopropanol and isobutanol, methanol and n-butanol, ethylene glycol and chloroform etc..
According to the present invention, the mass ratio of step (1) ferric flouride and sub- titanium oxide quality sum and solvent is 1:(5-
100) 1:5,1:10,1:20,1:30,1:40,1:50,1:60,1:70,1:80,1:90 or 1:100, Yi Jishang be can be, such as
The specific point value between numerical value is stated, as space is limited and for concise consideration, the present invention no longer exclusive list.
According to the present invention, step (1) carbon source be glucose, it is sucrose, cellulose, polyethylene glycol, polyvinyl alcohol, solvable
Property starch, monocrystal rock sugar, polycrystalline rock sugar, fructose, citric acid, phenolic resin, vinyl pyrrolidone, epoxy resin, glycan alcohol,
Any one in Kynoar, polyvinyl chloride, Lauxite, polymethacrylates or furane resins or at least two
Combination, such as can be glucose, sucrose, cellulose, polyethylene glycol, polyvinyl alcohol, soluble starch, monocrystal rock sugar, polycrystalline
Rock sugar, fructose, citric acid, phenolic resin, vinyl pyrrolidone, epoxy resin, glycan alcohol, Kynoar, polyvinyl chloride,
Any one in Lauxite, polymethacrylates or furane resins, typical but non-limiting combination are as follows: glucose and
Sucrose, polyethylene glycol and polyvinyl alcohol, soluble starch and monocrystal rock sugar, polycrystalline rock sugar and fructose, phenolic resin and asphalt mixtures modified by epoxy resin
Rouge, Kynoar and polyvinyl chloride, Lauxite and polymethacrylates etc..
According to the present invention, the temperature of step (2) described spray drying is 150-250 DEG C, such as can be 150 DEG C, 160
DEG C, 170 DEG C, 180 DEG C, 190 DEG C, 200 DEG C, 210 DEG C, 220 DEG C, 230 DEG C, between 240 DEG C or 250 DEG C and above-mentioned numerical value
Specific point value, as space is limited and for concise consideration, the present invention no longer exclusive list.
The third aspect, the present invention provide a kind of application of composite positive pole as described in relation to the first aspect, it is described it is compound just
Pole material is applied to lithium ion battery.
Compared with prior art, the present invention is at least had the advantages that
(1) present invention is jointly modified ferric flouride using sub- titanium oxide and carbon source, constructs multi-layer spherical structure, shape
Adult phase inside point contact type is compound with external face contact type, can mention to material overall conductivity and structural stability
It rises, and then improves the cycle performance and high rate performance of material.
(2) the advantages that the conductive height of Asia titanium oxide selected by the present invention, electrochemical stability and good corrosion resistance, and
Carbon material forms good mating reaction, can be effectively improved the electronic conductance of ferric flouride, improves the high rate performance of material, subtracts simultaneously
The generation of few side reaction, improves its chemical stability, and gained positive electrode is made still to be able to maintain preferable circulation at higher voltages
Stability and capacity retention ratio.
(3) for the present invention in composite particles coated with carbon source by the way of spray drying, prepared product is uniform
Degree is high, and consistency is good.
Detailed description of the invention
Fig. 1 is ferric flouride-Asia titanium oxide composite positive pole structural schematic diagram prepared by the embodiment of the present invention 1；Wherein,
1- carbon material, 2- are fluorinated iron particle, the Asia 3- titan oxide particles, 4-FeF3/T4O7。
The present invention is described in more detail below.But following examples is only simple example of the invention, not generation
Table or limitation the scope of the present invention, protection scope of the present invention are subject to claims.
Specific embodiment
To further illustrate the technical scheme of the present invention below with reference to the accompanying drawings and specific embodiments.
In order to better illustrate the present invention, it is easy to understand technical solution of the present invention, of the invention is typical but non-limiting
Embodiment is as follows:
Embodiment 1
(1) it disperses 20g ferric flouride and the Asia 2g titanium oxide in 200g water, a certain amount of sucrose is then added, obtain compound
Solution；
(2) composite solution that step (1) obtains is spray-dried at 250 DEG C, obtains composite positive pole, material
Middle carbon content is 20wt%.
As shown in Figure 1, resulting materials are the Multi-layer spherical structure that clad wraps up that kernel is formed, the kernel is ferric flouride
The compound and independent fluorination iron particle and sub- titan oxide particles formed with sub- titanium oxide.
Electrochemical property test is carried out using resulting materials as anode material for lithium-ion batteries, pole piece proportion is composite wood
Material: acetylene black: PVDF=80:10:10.Using lithium piece as reference electrode, CR2025 type button cell is prepared.In 2-4.5V voltage window
Mouthful, under 50mA/g current density, recycling specific discharge capacity for the first time is 215mAh/g, 200 circle capacity retention ratio 92% of circulation.
Embodiment 2
(1) it disperses 2g ferric flouride and the Asia 0.1g titanium oxide in 200g alcohol, a certain amount of polyethylene glycol is then added, obtains
To composite solution；
(2) composite solution that step (1) obtains is spray-dried at 150 DEG C, obtains composite positive pole, material
Middle carbon content is 40wt%.
Electrochemical property test is carried out using resulting materials as anode material for lithium-ion batteries, pole piece proportion is composite wood
Material: acetylene black: PVDF=80:10:10.Using lithium piece as reference electrode, CR2025 type button cell is prepared.In 2-4.5V voltage window
Mouthful, under 50mA/g current density, recycling specific discharge capacity for the first time is 193mAh/g, 200 circle capacity retention ratio 91% of circulation.
Embodiment 3
(1) it disperses 0.5g ferric flouride and the Asia 0.05g titanium oxide in 5g n-butanol, a certain amount of citric acid is then added,
Obtain composite solution；
(2) composite solution that step (1) obtains is spray-dried at 200 DEG C, obtains composite positive pole, material
Middle carbon content is 10wt%.
Electrochemical property test is carried out using resulting materials as anode material for lithium-ion batteries, pole piece proportion is composite wood
Material: acetylene black: PVDF=80:10:10.Using lithium piece as reference electrode, CR2025 type button cell is prepared.In 2-4.5V voltage window
Mouthful, under 50mA/g current density, recycling specific discharge capacity for the first time is 185mAh/g, 200 circle capacity retention ratio 89% of circulation.
Embodiment 4
(1) it disperses 400g ferric flouride and the Asia 10g titanium oxide in 4000g ethylene glycol, a certain amount of asphalt mixtures modified by epoxy resin is then added
Rouge obtains composite solution；
(2) composite solution that step (1) obtains is spray-dried at 210 DEG C, obtains composite positive pole, material
Middle carbon content is 5wt%.
Electrochemical property test is carried out using resulting materials as anode material for lithium-ion batteries, pole piece proportion is composite wood
Material: acetylene black: PVDF=80:10:10.Using lithium piece as reference electrode, CR2025 type button cell is prepared.In 2-4.5V voltage window
Mouthful, under 50mA/g current density, recycling specific discharge capacity for the first time is 198mAh/g, 200 circle capacity retention ratio 91% of circulation.
Embodiment 5
(1) it disperses 40g ferric flouride and the Asia 6g titanium oxide in 400g propyl alcohol, a certain amount of glycan alcohol is then added, obtains
Composite solution；
(2) composite solution that step (1) obtains is spray-dried at 250 DEG C, obtains composite positive pole, material
Middle carbon content is 30wt%.
Electrochemical property test is carried out using resulting materials as anode material for lithium-ion batteries, pole piece proportion is composite wood
Material: acetylene black: PVDF=80:10:10.Using lithium piece as reference electrode, CR2025 type button cell is prepared.In 2-4.5V voltage window
Mouthful, under 50mA/g current density, recycling specific discharge capacity for the first time is 202mAh/g, 200 circle capacity retention ratio 90% of circulation.
Embodiment 6
(1) it disperses 50g ferric flouride and the Asia 3g titanium oxide in 1000g chloroform, a certain amount of soluble starch is then added,
Obtain composite solution；
(2) composite solution that step (1) obtains is spray-dried at 150 DEG C, obtains composite positive pole, material
Middle carbon content is 10wt%.
Electrochemical property test is carried out using resulting materials as anode material for lithium-ion batteries, pole piece proportion is composite wood
Material: acetylene black: PVDF=80:10:10.Using lithium piece as reference electrode, CR2025 type button cell is prepared.In 2-4.5V voltage window
Mouthful, under 50mA/g current density, recycling specific discharge capacity for the first time is 195mAh/g, 200 circle capacity retention ratio 91% of circulation.
Comparative example 1
(1) it disperses 20g ferric flouride in 200g water, a certain amount of sucrose is then added, obtains composite solution；
(2) composite solution that step (1) obtains is spray-dried at 250 DEG C, obtains composite material, carbon in material
Content is 20wt%.
Electrochemical property test is carried out using resulting materials as anode material for lithium-ion batteries, pole piece proportion is composite wood
Material: acetylene black: PVDF=80:10:10.Using lithium piece as reference electrode, CR2025 type button cell is prepared.In 2-4.5V voltage window
Mouthful, under 50mA/g current density, recycling specific discharge capacity for the first time is 210mAh/g, 200 circle capacity retention ratio 73% of circulation.
Comparative example 2
(1) it disperses 20g ferric flouride and the Asia 2g titanium oxide in 200g water, obtains composite solution；
(2) composite solution that step (1) obtains is spray-dried at 250 DEG C, obtains composite positive pole.
Electrochemical property test is carried out using resulting materials as anode material for lithium-ion batteries, pole piece proportion is composite wood
Material: acetylene black: PVDF=80:10:10.Using lithium piece as reference electrode, CR2025 type button cell is prepared.In 2-4.5V voltage window
Mouthful, under 50mA/g current density, recycling specific discharge capacity for the first time is 215mAh/g, 200 circle capacity retention ratio 45% of circulation.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail within the scope of the technical concept of the present invention can be with various simple variants of the technical solution of the present invention are made, this
A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case where shield, can be combined in any appropriate way, in order to avoid unnecessary repetition, the present invention to it is various can
No further explanation will be given for the combination of energy.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should also be regarded as the disclosure of the present invention.
Claims (10)
1. a kind of ferric flouride-Asia titanium oxide composite positive pole, which is characterized in that the composite positive pole is spherical structure,
Including kernel and clad, the kernel is ferric flouride and sub- titanium oxide, and the clad is carbon material.
2. composite positive pole as described in claim 1, which is characterized in that based on mass percentage, the anode composite
The content of material Central Asia titanium oxide is 1-15%；
Preferably, based on mass percentage, the content of carbon material is 1-40% in the composite positive pole.
3. composite positive pole as claimed in claim 1 or 2, which is characterized in that the partial size of the composite positive pole is 1-
20μm。
4. composite positive pole as described in any one of claims 1-3, which is characterized in that ferric flouride and sub- oxygen in the kernel
Change titanium to exist in the form of compound, fluorination iron particle and sub- titan oxide particles；
Preferably, the structural formula of the ferric flouride and sub- titanium oxide compound is FeF3/T4O7, the partial size of the compound is
0.9-9μm；
Preferably, the partial size of the fluorination iron particle is 0.5-5 μm；
Preferably, the partial size of the sub- titan oxide particles is 0.5-5 μm.
5. the preparation method of composite positive pole according to any one of claims 1-4, which is characterized in that the method includes
Following steps:
(1) it disperses ferric flouride and sub- titanium oxide in solvent by formula ratio, carbon source is then added, obtains composite solution；
(2) composite solution that step (1) obtains is spray-dried, obtains the composite positive pole.
6. method as claimed in claim 5, which is characterized in that step (1) solvent is water, ethyl alcohol, acetone, propyl alcohol, different
In propyl alcohol, isobutanol, methanol, n-butanol, ethylene glycol or chloroform any one or at least two combination.
7. such as method described in claim 5 or 6, which is characterized in that step (1) ferric flouride and sub- titanium oxide quality sum
Mass ratio with solvent is 1:(5-100).
8. such as the described in any item methods of claim 5-7, which is characterized in that step (1) carbon source be glucose, sucrose,
Cellulose, polyethylene glycol, polyvinyl alcohol, soluble starch, monocrystal rock sugar, polycrystalline rock sugar, fructose, citric acid, phenolic resin, second
Vinyl pyrrolidone, epoxy resin, glycan alcohol, Kynoar, polyvinyl chloride, Lauxite, polymethacrylates or furan
In furane resins any one or at least two combination.
9. such as the described in any item methods of claim 5-8, which is characterized in that the temperature of step (2) described spray drying is
150-250℃。
10. the application of composite positive pole according to any one of claims 1-4, which is characterized in that the anode composite material
Material is applied to lithium ion battery.
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| CN201811276636.3A CN109449408B (en) | 2018-10-30 | 2018-10-30 | Ferric fluoride-titanium suboxide composite positive electrode material and preparation method and application thereof |
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| CN201811276636.3A CN109449408B (en) | 2018-10-30 | 2018-10-30 | Ferric fluoride-titanium suboxide composite positive electrode material and preparation method and application thereof |
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| CN109449408B CN109449408B (en) | 2021-08-17 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110444748A (en) * | 2019-07-29 | 2019-11-12 | 贵州梅岭电源有限公司 | A kind of FeF3Composite positive pole and preparation method thereof |
Citations (5)
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| CN109449408B (en) | 2021-08-17 |
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