CN108110218A - A kind of lithium battery anode structure and preparation method thereof - Google Patents
A kind of lithium battery anode structure and preparation method thereof Download PDFInfo
- Publication number
- CN108110218A CN108110218A CN201711371333.5A CN201711371333A CN108110218A CN 108110218 A CN108110218 A CN 108110218A CN 201711371333 A CN201711371333 A CN 201711371333A CN 108110218 A CN108110218 A CN 108110218A
- Authority
- CN
- China
- Prior art keywords
- thin film
- film layer
- collecting body
- plate current
- lithium battery
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 46
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000002245 particle Substances 0.000 claims abstract description 75
- 239000010409 thin film Substances 0.000 claims abstract description 73
- 229910001512 metal fluoride Inorganic materials 0.000 claims abstract description 45
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 37
- 229910052799 carbon Inorganic materials 0.000 claims description 33
- 239000000463 material Substances 0.000 claims description 28
- 238000000576 coating method Methods 0.000 claims description 11
- 238000005516 engineering process Methods 0.000 claims description 11
- 238000007740 vapor deposition Methods 0.000 claims description 11
- 239000011248 coating agent Substances 0.000 claims description 10
- 238000003786 synthesis reaction Methods 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 230000008021 deposition Effects 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- 229910021583 Cobalt(III) fluoride Inorganic materials 0.000 claims description 5
- 238000001704 evaporation Methods 0.000 claims description 3
- 230000008020 evaporation Effects 0.000 claims description 3
- 239000000758 substrate Substances 0.000 claims description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims 1
- 239000004744 fabric Substances 0.000 claims 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims 1
- 239000010931 gold Substances 0.000 claims 1
- 229910052737 gold Inorganic materials 0.000 claims 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 abstract description 4
- 239000011737 fluorine Substances 0.000 abstract description 4
- 229910052731 fluorine Inorganic materials 0.000 abstract description 4
- 230000003647 oxidation Effects 0.000 abstract description 4
- 238000007254 oxidation reaction Methods 0.000 abstract description 4
- 229910021561 transition metal fluoride Inorganic materials 0.000 abstract description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 46
- 238000000034 method Methods 0.000 description 10
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 229910001416 lithium ion Inorganic materials 0.000 description 6
- 238000001035 drying Methods 0.000 description 5
- 238000000151 deposition Methods 0.000 description 4
- 239000008187 granular material Substances 0.000 description 4
- 230000008439 repair process Effects 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 238000001027 hydrothermal synthesis Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 230000005012 migration Effects 0.000 description 3
- 238000013508 migration Methods 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 239000007767 bonding agent Substances 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- WZJQNLGQTOCWDS-UHFFFAOYSA-K cobalt(iii) fluoride Chemical compound F[Co](F)F WZJQNLGQTOCWDS-UHFFFAOYSA-K 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000009831 deintercalation Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- OTTGETCGDDGTDM-UHFFFAOYSA-N iron trifluoroborane Chemical compound [Fe].B(F)(F)F OTTGETCGDDGTDM-UHFFFAOYSA-N 0.000 description 2
- 235000019353 potassium silicate Nutrition 0.000 description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 description 2
- 239000012279 sodium borohydride Substances 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000010025 steaming Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910012820 LiCoO Inorganic materials 0.000 description 1
- 229910010710 LiFePO Inorganic materials 0.000 description 1
- 229910015645 LiMn Inorganic materials 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 239000010450 olivine Substances 0.000 description 1
- 229910052609 olivine Inorganic materials 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- -1 stalk Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
-
- 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
- H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
-
- 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 technical field of lithium batteries more particularly to a kind of lithium battery anode structure and preparation method thereof.A kind of lithium battery anode structure, including plus plate current-collecting body and the anode thin film layer being formed on the plus plate current-collecting body, the anode thin film layer includes metal fluoride Fe1‑xCoxF3Particle.The electronegativity of fluorine is strong, free energy is larger, the binary transition metal fluoride Fe formed1‑xCoxF3M F ion bond strengths it is higher, and metallic oxidation state is higher, its discharge potential platform is higher, generally 1.5 4.5V, when it is formed on the plus plate current-collecting body, so that the plus plate current-collecting body has high specific capacity, and then the lithium battery comprising the plus plate current-collecting body for being formed with anode thin film layer has higher energy density.
Description
【Technical field】
The present invention relates to technical field of lithium batteries more particularly to a kind of lithium battery anode structure and preparation method thereof.
【Background technology】
Commercialization lithium battery generally uses embedding de- lithium material as anode at present, such as the LiCoO of layer structure2, spinelle knot
The LiMn of structure2O4With the LiFePO of olivine structural4Graphite type material is used Deng, negative material.Above-mentioned electrode material is to pass through lithium
The intercalation/deintercalation of ion transmits electric current, and in reaction process, lithium ion reversibly deintercalation between positive and negative anodes occurs homogeneous
Reaction, the structure of matter do not change.It is limited by cathode material structure, the saturation embedded quantity of lithium ion is limited, therefore every
The amount of lithium ions that secondary charge and discharge cycles exchange is limited, causes its specific discharge capacity relatively low.In recent years, electric tool, electric boosted
The rapid development of vehicle, the particularly fields such as electric vehicle provides good application prospect for lithium battery, but simultaneously to lithium battery
The performances such as cycle life, energy density, security, price and Environmental compatibility propose higher requirement.Therefore tradition
Graphite cathode and positive electrode have been unable to meet the requirement of growing energy density, be badly in need of developing new high power capacity just
Negative electrode material.
【The content of the invention】
To overcome, to have been unable to meet growing lithium battery high-energy close for traditional graphite cathode and positive electrode at present
The requirement of degree, the present invention provide the lithium battery anode structure and its preparation that a kind of specific volume metric density is high, charge and discharge cycles effect is good
Method.
In order to solve the above-mentioned technical problem the present invention, provides a technical solution：A kind of lithium battery anode structure, including anode
Collector and the anode thin film layer being formed on the plus plate current-collecting body, the anode thin film layer include metal fluoride Fe1- xCoxF3Particle.
Preferably, the thickness of the anode thin film layer is 1-100 μm.
In order to solve the above-mentioned technical problem the present invention, provides another technical solution：One plus plate current-collecting body is provided, is then utilized
Physical vaporous deposition forms the anode thin film layer on the plus plate current-collecting body, and the anode thin film layer includes metal pentafluoride
Object Fe1-xCoxF3Particle, concretely comprise the following steps：
A plus plate current-collecting body is provided as substrate；
FeF is installed3And CoF3Steaming；
Vacuum is extracted into 5 X 10-3Below Pa；
Vapor deposition temperature is adjusted to 200-1000 DEG C；
Adjusting air pressure is 0.1-10Pa, vapor deposition power is：10-300W is deposited, evaporation time 0.1-2h.
Preferably, vapor deposition power is preferably：150W.In order to solve the above-mentioned technical problem the present invention, provides another technical side
Case：A kind of lithium battery anode structure, including plus plate current-collecting body and the anode thin film layer being formed on the plus plate current-collecting body, institute
Stating anode thin film layer includes metal fluoride Fe1-xCoxF3Particle, the metal fluoride included by the anode thin film layer
Fe1-xCoxF3Particle surface be formed with carbon decorative layer.
Preferably, the thickness of the carbon decorative layer is 1-100nm.
Preferably, the thickness of the anode thin film layer is 1-100 μm.
In order to solve the above-mentioned technical problem the present invention, provides another technical solution：A kind of preparation of lithium battery anode structure
Method comprises the following steps：It is obtained using chemical synthesis described including metal fluoride Fe1-xCoxF3Particle, recycle
CVD technology is described including metal fluoride Fe1-xCoxF3Particle surface formed carbon decorative layer, obtain positive electrode particle material, so
The positive electrode particle material is coated on the plus plate current-collecting body by way of coating afterwards, after drying process, is formed
Anode thin film layer.
Preferably, it is described to utilize CVD technology described including metal fluoride Fe1-xCoxF3Particle surface formed carbon repair
The step of adoring layer is specific as follows：
By N2And C3H6Mixture is added to containing the Fe obtained using chemical synthesis1-xCoxF3The pre- thermal inertia of particle is anti-
It answers in stove；
Reaction temperature is set as 700-1000 DEG C, 0.1~1h of time, obtains metal fluoride Fe1-xCoxF3Particle surface
It is formed with the positive electrode particle material of carbon decorative layer.
Compared with the prior art, the anode thin film layer includes metal fluoride Fe1-xCoxF3Particle.The electronegativity of fluorine is strong,
Free energy is larger, the binary transition metal fluoride Fe formed1-xCoxF3M-F ionic bond intensity it is higher, and clipped wire
Sub- oxidation state is higher, and discharge potential platform is higher, generally 1.5-4.5V, and then include the lithium battery of the anode thin film layer
With higher energy density.
The anode thin film layer is directly formed on the plus plate current-collecting body using vacuum vapor deposition method, facilitates preparation miniature lithium
Battery and wearable device, while facilitate the laminated construction for preparing solid lithium battery.
Power, which is deposited, is preferably：150W.So that the anode thin film layer being formed on the plus plate current-collecting body is dense,
Fine and close anode thin film layer structure is formed, reduces the migration impedance of lithium ion, is reduced between anode thin film layer and plus plate current-collecting body
Interface impedance.
The metal fluoride Fe1-xCoxF3Particle surface be formed with carbon decorative layer formed positive electrode particle material, when by this just
When pole granular materials is coated on formation anode thin film layer on the plus plate current-collecting body, the electricity of anode thin film layer can be improved well
Electron conductivity, and then enhance utilize the multiplying power property for being formed with the anode thin film layer lithium battery well.
In order to solve the above-mentioned technical problem the present invention, provides another technical solution：A kind of lithium battery anode structure, including just
Pole collector and the anode thin film layer being formed on the plus plate current-collecting body, the anode thin film layer include metal fluoride
Fe1-xCoxF3Particle, the metal fluoride Fe included by the anode thin film layer1-xCoxF3Particle surface be formed with carbon and repair
Adorn layer.Carbon decorative layer can improve the electronic conductivity of the anode thin film layer well.
In order to solve the above-mentioned technical problem the present invention, provides another technical solution：The bag is obtained using chemical synthesis
Include metal fluoride Fe1-xCoxF3Particle, recycle CVD technology described including metal fluoride Fe1-xCoxF3Particle table
Face forms carbon decorative layer, obtains positive electrode particle material, and the positive electrode particle material then is coated with pole pole by way of coating
On piece collector, after drying process, anode thin film layer is formed.The carbon decorative layer is formed in using CVD technology described
Including metal fluoride Fe1-xCoxF3Particle surface on, well ensure carbon decorative layer compactness, uniformity.Carbon is modified
Layer is effectively improved the electronic conductance of the anode thin film layer, improves the multiplying power property of battery.
【Description of the drawings】
Fig. 1 is the overall structure diagram of lithium battery anode structure in first embodiment in the present invention；
Fig. 2 is the flow chart for preparing lithium battery anode structure in the present invention in first embodiment；
Fig. 3 is the overall structure diagram of lithium battery anode structure in second embodiment in the present invention；
Fig. 4 is positive electrode particle material schematic cross-sectional view in second embodiment in the present invention；
Fig. 5 is that carbon decorative layer is formed in comprising metal fluoride Fe in second embodiment in the present invention1-xCoxF3Particle
The flow chart on surface.
【Specific embodiment】
In order to make the purpose of the present invention, technical solution and advantage are more clearly understood, with reference to the accompanying drawings and embodiments, right
The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and
It is not used in the restriction present invention.
First embodiment, referring to Fig. 1, a kind of lithium battery anode structure 10, including plus plate current-collecting body 100 and is formed in institute
The anode thin film layer 200 on plus plate current-collecting body 100 is stated, the anode thin film layer 200 includes metal fluoride Fe1-xCoxF3(0<
x<1) particle 201.
A kind of method for preparing lithium battery anode structure including providing a plus plate current-collecting body 100, then utilizes physical vapor
Sedimentation forms the anode thin film layer 200 on the plus plate current-collecting body 100, and the anode thin film layer 200 includes metal fluorine
Compound Fe1-xCoxF3Particle 201.
Referring to Fig. 2, the utilization physical vaporous deposition is specially vacuum vapour deposition, it is described to be existed using vacuum vapour deposition
The step of forming anode thin film layer 200 on the plus plate current-collecting body 100 is specific as follows：
A1：A plus plate current-collecting body 100 is provided as substrate；
A2：FeF is installed3And CoF3Steaming；
A3：Vacuum is extracted into 5 X 10-3Below Pa；
A4：Vapor deposition temperature is adjusted to 200-1000 DEG C；
A5：Adjusting air pressure is 0.1-10Pa, and vapor deposition power is：10-300W is deposited, and evaporation time is 0.1~2h.
In above-mentioned steps A1, in selected 100 aluminium of plus plate current-collecting body, stainless steel, nickel, molybdenum, titanium, niobium, copper, iron
It is any.
In above-mentioned steps A5, vapor deposition power is preferably 150W.
Incorporated by reference to Fig. 1 and Fig. 2, after being finished through above-mentioned steps A5 vapor depositions, it is formed on the plus plate current-collecting body 100
The thickness of anode thin film layer 200 is 1-100 μm.Anode thin film layer 200 includes metal fluoride Fe1-xCoxF3Particle 201.Fluorine
Electronegativity is strong, free energy is larger, and the M-F ionic bond intensity of the binary transition metal fluoride formed is higher, and metal
Particle oxidation state is higher, and discharge potential platform is higher, and generally 1.5-4.5V, 200 specific capacity of anode thin film layer can reach
700mAh/g。
Second embodiment, refers to Fig. 3 and Fig. 4, a kind of lithium battery anode structure 20, which includes
Plus plate current-collecting body 100 and the anode thin film layer 200 being formed on the plus plate current-collecting body 100, the anode thin film layer 200 wrap
Include metal fluoride Fe1-xCoxF3Particle 201, the metal fluoride Fe included by the anode thin film layer 2001-xCoxF3's
201 surface of particle is formed with carbon decorative layer 202, described including metal fluoride Fe1-xCoxF3201 surface of particle formed carbon repair
It adorns after layer 202, obtains the positive electrode particle material 203 being coated on plus plate current-collecting body 100.
Plus plate current-collecting body employed in the structure and first embodiment of plus plate current-collecting body 100 employed in the present embodiment
100 structures are identical, and it is no longer repeated herein.
A kind of preparation method of lithium battery anode structure, comprises the following steps：Using chemical synthesis obtain described in include
Metal fluoride Fe1-xCoxF3Particle 201, recycle CVD technology described including metal fluoride Fe1-xCoxF3Particle
201 surfaces form carbon decorative layer 202, positive electrode particle material 203 are obtained, then by the positive electrode particle material by way of coating
Material 203 is coated on the plus plate current-collecting body 100, forms anode thin film layer 200.
Utilization chemical synthesis described above obtains described including metal fluoride Fe1-xCoxF3Particle 201 can be
Any one of high temperature solid phase synthesis, hydrothermal synthesis method, solvent-thermal method, liquid-phase coprecipitation, microwave process for synthesizing.This embodiment party
In formula, hydrothermal synthesis method is selected to be specifically described：Synthesis material mainly has：Ethyl orthosilicate, sodium borohydride, borontrifluoride iron,
Cobalt trifluoride, silane coupling agent, waterglass, stalk, citric acid and distilled water.
It is obtained using hydrothermal synthesis method described including metal fluoride Fe1-xCoxF3Particle 201 concretely comprise the following steps：
B1：Stalk is ground into tiny graininess, is dried after cleaning up, moisture is controlled in 20-25% or so；
B2：Citric acid is added in distilled water, be stirring evenly and then adding into through the dried stalks of B1 impregnate 4-8 it is small when,
Obtain stalk mixture；
B3：It will be added to after the drying water removal of stalk mixture in retort, when first low-temperature carbonization 1-2 is small at 250-350 DEG C,
Then temperature is raised to 450-550 DEG C, and stalk dried object is obtained after continuing carbonization 1-2h；
B4：Ethyl orthosilicate, silane coupling agent and waterglass are added in distilled water, 60-70 DEG C is heated to and stirs evenly,
Along with the stalk dried object obtained in borontrifluoride iron, cobalt trifluoride, sodium borohydride and step V3, be stirred to react 1-2 it is small when,
Be added to after reaction in microwave drying at 130-150 DEG C dry 3-5 it is small when, acquisition includes metal fluoride Fe1-xCoxF3's
Particle 201.
Referring to Fig. 5, include metal fluoride Fe by being obtained in B41-xCoxF3Particle 201 using CVD technology described
Including metal fluoride Fe1-xCoxF3201 surface of particle formed carbon decorative layer 202 the step of it is specific as follows：
C1：By N2 and C3H6Mixture is added to containing the Fe obtained using chemical synthesis1-xCoxF3Nano particle it is lazy
In the pre- thermal reaction furnace of property；
C2：Reaction temperature is set as 700-1000 DEG C, 0.1~1h of time, obtains metal fluoride Fe1-xCoxF3Particle
Surface is formed with the positive electrode particle material of carbon decorative layer.
Positive electrode particle material 203 obtained in above-mentioned steps C2 includes Fe containing metal fluoride1-xCoxF3Particle 201
With the carbon decorative layer 202 being formed on the particle 201, the thickness of the carbon decorative layer 202 is 1-100nm.
Described above is coated on the plus plate current-collecting body 100 by way of coating by the positive electrode particle material 203
On, forming the coating method of anode thin film layer 200 can be：Spraying, slot coated, transfer coated, micro- intaglio plate coating, dipping carry
Draw any one of coating, blade coating.
The positive electrode particle material 203 is coated on the plus plate current-collecting body 100 by way of coating, forms anode
The step of film layer 200, is specific as follows：
D1：Positive electrode particle material 203 and conductive agent, acetylene black, bonding agent are mixed, obtain granulate mixture；
D2：With the granulate mixture obtained in organic dissolution D1, slurry is formed；
D3：The slurry obtained in D2 is coated on the plus plate current-collecting body 100；
D4：The plus plate current-collecting body 100 that slurry is coated in D3 is dried, obtains being formed in the plus plate current-collecting body
Anode thin film layer 200 on 100.
The main purpose that conductive agent is added in above-mentioned steps D1 is to ensure to be formed with the anode of the anode thin film layer 200
Collector 100 has preferable charge-discharge performance, when plus plate current-collecting body 100 makes, is usually added into a certain amount of conductive materials,
It is micro- that collection is played between the active material included by plus plate current-collecting body 100, between active material and plus plate current-collecting body 1001
The effect of electric current to reduce the contact resistance of plus plate current-collecting body 100 and electrolyte, accelerates the rate travel of conductive ion, simultaneously
Also migration rate of the conductive lithium ion in plus plate current-collecting body 100 is effectively improved, so as to improve the charge and discharge of plus plate current-collecting body 100
Electrical efficiency.
The purpose mainly enhancing for adding in acetylene black and the mixing of positive electrode particle material 203 is formed with the anode thin film layer 200
Plus plate current-collecting body 100 electric conductivity, thermal conductivity and antistatic effect, improve the specific capacity of the plus plate current-collecting body 100.
As long as the purpose of the bonding agent of addition so that the slurry be preferably coated on the plus plate current-collecting body 100 it
On.
The organic dissolution added in step D2 is mainly NMP (- 2 pyrrolidones of 1- methyl).
The thickness of anode thin film layer 200 formed in above-mentioned steps D4 is 1-100 μm.
In the present embodiment, described including metal fluoride Fe1-xCoxF3201 surface of particle be formed with carbon decorative layer
202, so as to which the main function for obtaining positive electrode particle material 203 is：Improve the metal fluoride Fe1-xCoxF3Particle 201
Electronic conductance so that be formed in the anode thin film layer 200 on the plus plate current-collecting body 100 sheet resistance reduce, and then,
So that the lithium battery high rate performance for being formed with the anode thin film layer 200 is promoted.
Compared with the prior art, the anode thin film layer includes metal fluoride Fe1-xCoxF3Particle.The electronegativity of fluorine is strong,
Free energy is larger, the binary transition metal fluoride Fe formed1-xCoxF3M-F ionic bond intensity it is higher, and clipped wire
Sub- oxidation state is higher, and discharge potential platform is higher, generally 1.5-4.5V, and then include the lithium battery of the anode thin film layer
With higher energy density.
The anode thin film layer is directly formed on the plus plate current-collecting body using vacuum vapor deposition method, facilitates preparation miniature lithium
Battery and wearable device, while facilitate the laminated construction for preparing solid lithium battery.
Power, which is deposited, is preferably：150W.So that the anode thin film layer being formed on the plus plate current-collecting body is dense,
Fine and close anode thin film layer structure is formed, reduces the migration impedance of lithium ion, is reduced between anode thin film layer and plus plate current-collecting body
Interface impedance.
The metal fluoride Fe1-xCoxF3Particle surface be formed with carbon decorative layer formed positive electrode particle material, when by this just
When pole granular materials is coated on formation anode thin film layer on the plus plate current-collecting body, the electricity of anode thin film layer can be improved well
Electron conductivity, and then enhance utilize the multiplying power property for being formed with the anode thin film layer lithium battery well.
In order to solve the above-mentioned technical problem the present invention, provides another technical solution：A kind of lithium battery anode structure, including just
Pole collector and the anode thin film layer being formed on the plus plate current-collecting body, the anode thin film layer include metal fluoride
Fe1-xCoxF3Particle, the metal fluoride Fe included by the anode thin film layer1-xCoxF3Particle surface be formed with carbon and repair
Adorn layer.Carbon decorative layer can improve the electronic conductivity of the anode thin film layer well.
In order to solve the above-mentioned technical problem the present invention, provides another technical solution：The bag is obtained using chemical synthesis
Include metal fluoride Fe1-xCoxF3Particle, recycle CVD technology described including metal fluoride Fe1-xCoxF3Particle table
Face forms carbon decorative layer, obtains positive electrode particle material, and the positive electrode particle material then is coated with pole pole by way of coating
On piece collector, after drying process, anode thin film layer is formed.The carbon decorative layer is formed in using CVD technology described
Including metal fluoride Fe1-xCoxF3Particle surface on, well ensure carbon decorative layer compactness, uniformity.Carbon is modified
Layer is effectively improved the electronic conductance of the anode thin film layer, improves the multiplying power property of battery.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all originals in the present invention
Any modification made within then, equivalent substitution and improvement etc. should all be included within protection scope of the present invention.
Claims (10)
1. a kind of lithium battery anode structure, it is characterised in that：Including plus plate current-collecting body and it is formed on the plus plate current-collecting body
Anode thin film layer, the anode thin film layer include metal fluoride Fe1-xCoxF3Particle.
2. lithium battery anode structure as described in claim 1, it is characterised in that：The thickness of the anode thin film layer is 1-100 μ
m。
3. a kind of lithium battery anode structure, it is characterised in that：Including plus plate current-collecting body and it is formed on the plus plate current-collecting body
Anode thin film layer, the anode thin film layer include metal fluoride Fe1-xCoxF3Particle, included by the anode thin film layer
Metal fluoride Fe1-xCoxF3Particle surface be formed with carbon decorative layer.
4. lithium battery anode structure as claimed in claim 3, it is characterised in that：The thickness of the carbon decorative layer is 1-100nm.
5. lithium battery anode structure as claimed in claim 3, it is characterised in that：The thickness of the anode thin film layer is 1-100 μ
m。
6. a kind of preparation method of lithium battery anode structure, it is characterised in that comprise the following steps：A plus plate current-collecting body is provided, so
The anode thin film layer is formed on the plus plate current-collecting body using physical vaporous deposition afterwards, the anode thin film layer includes gold
Belong to fluoride Fe1-xCoxF3Particle.
7. the preparation method of lithium battery anode structure as claimed in claim 6, it is characterised in that：The physical vaporous deposition
Specially vacuum vapour deposition, the anode thin film layer are formed on plus plate current-collecting body by vacuum vapour deposition, concretely comprised the following steps：
A plus plate current-collecting body is provided as substrate；
FeF is installed3And CoF3Target；
Vacuum is extracted into 5 X 10-3Below Pa；
Vapor deposition temperature is adjusted to 200-1000 DEG C；
Adjusting air pressure is 0.1-10Pa, and vapor deposition power is：10-300W is deposited, 0.1~2h of evaporation time.
8. the preparation method of lithium battery anode structure as claimed in claim 7, it is characterised in that：Power, which is deposited, is preferably：
150W。
9. a kind of preparation method of lithium battery anode structure, it is characterised in that comprise the following steps：It is obtained using chemical synthesis
It is described including metal fluoride Fe1-xCoxF3Particle, recycle CVD technology described including metal fluoride Fe1-xCoxF3's
Particle surface forms carbon decorative layer, obtains positive electrode particle material, is then applied the positive electrode particle material by way of coating
Cloth forms anode thin film layer on the plus plate current-collecting body.
10. the preparation method of lithium battery anode structure as claimed in claim 9, it is characterised in that：It is described to be existed using CVD technology
It is described including metal fluoride Fe1-xCoxF3Particle surface formed carbon decorative layer the step of it is specific as follows：
By N2And C3H6Mixture is added to containing the Fe obtained using chemical synthesis1-xCoxF3The preheating inert reaction stove of particle
In；
Reaction temperature is set as 700-1000 DEG C, 0.1~1h of time, obtains metal fluoride Fe1-xCoxF3Particle surface formed
There is the positive electrode particle material of carbon decorative layer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711371333.5A CN108110218A (en) | 2017-12-19 | 2017-12-19 | A kind of lithium battery anode structure and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711371333.5A CN108110218A (en) | 2017-12-19 | 2017-12-19 | A kind of lithium battery anode structure and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108110218A true CN108110218A (en) | 2018-06-01 |
Family
ID=62210073
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711371333.5A Pending CN108110218A (en) | 2017-12-19 | 2017-12-19 | A kind of lithium battery anode structure and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108110218A (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102315482A (en) * | 2011-08-31 | 2012-01-11 | 北京理工大学 | Lithium secondary battery with metal fluoride as positive electrode material |
| CN102623707A (en) * | 2012-04-02 | 2012-08-01 | 湘潭大学 | Cobalt-doped carbon-coated ferric fluoride anode material and preparation method thereof |
| CN106848252A (en) * | 2017-03-16 | 2017-06-13 | 成都新柯力化工科技有限公司 | One kind evaporation aluminum fluoride improves the durothermic method of ternary anode material of lithium battery |
| CN207602682U (en) * | 2017-12-19 | 2018-07-10 | 成都亦道科技合伙企业（有限合伙） | A kind of lithium battery anode structure |
-
2017
- 2017-12-19 CN CN201711371333.5A patent/CN108110218A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102315482A (en) * | 2011-08-31 | 2012-01-11 | 北京理工大学 | Lithium secondary battery with metal fluoride as positive electrode material |
| CN102623707A (en) * | 2012-04-02 | 2012-08-01 | 湘潭大学 | Cobalt-doped carbon-coated ferric fluoride anode material and preparation method thereof |
| CN106848252A (en) * | 2017-03-16 | 2017-06-13 | 成都新柯力化工科技有限公司 | One kind evaporation aluminum fluoride improves the durothermic method of ternary anode material of lithium battery |
| CN207602682U (en) * | 2017-12-19 | 2018-07-10 | 成都亦道科技合伙企业（有限合伙） | A kind of lithium battery anode structure |
Non-Patent Citations (1)
| Title |
|---|
| LI LIU等: "Excellent cycle performance of Co-doped FeF3/C nanocomposite cathode material for lithium-ion batteries" * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107425185B (en) | Preparation method of carbon nanotube-loaded molybdenum carbide material and application of carbon nanotube-loaded molybdenum carbide material in lithium-sulfur battery positive electrode material | |
| CN108649190A (en) | Vertical graphene with three-dimensional porous array structure/titanium niobium oxygen/sulphur carbon composite and its preparation method and application | |
| CN102832392A (en) | Current collector carbon coated aluminum foil and its preparation method | |
| CN107623116A (en) | A kind of composite cathode material of lithium ion battery and preparation method thereof | |
| CN110197899B (en) | Preparation method of lithium foil | |
| CN108390035A (en) | The preparation method of graphene/trielement composite material | |
| CN105742695B (en) | A kind of lithium ion battery and preparation method thereof | |
| CN105932236B (en) | A kind of coating modification method of lithium ion battery electrode material | |
| CN108321438B (en) | Full-graphite lithium-sulfur battery and preparation method thereof | |
| CN111540889B (en) | Silicon negative electrode material coated by double-layer coating layer and preparation method and application thereof | |
| CN110957490A (en) | Preparation method of carbon-coated sodium iron phosphate electrode material with hollow structure | |
| WO2017121113A1 (en) | Carbon-coated zinc ferrite electrode material, and preparation method and application thereof | |
| CN108336312A (en) | A kind of silicon-carbon cathode material preparation method of high first effect long-life | |
| CN104103821A (en) | Preparation method for silicon-carbon anode material | |
| CN111276674A (en) | Modified graphite negative electrode material, preparation method thereof and battery containing modified graphite negative electrode | |
| CN111517374A (en) | Fe7S8Preparation method of/C composite material | |
| CN107658461B (en) | Method for preparing ferric fluoride/carbon composite material by taking organic iron compound as raw material | |
| WO2019047010A1 (en) | Double layer-coated nano-silicon negative electrode material, preparation method therefor and use thereof | |
| CN106876684A (en) | A kind of lithium battery silicium cathode material, negative plate and the lithium battery prepared with it | |
| CN108899499A (en) | Based on phosphatic negative electrode material of Sb/Sn and preparation method thereof and the application in sodium-ion battery | |
| CN110311111A (en) | N adulterates CNT in-stiu coating Co nano particle composite material and preparation and application | |
| CN104300113A (en) | Carbon-coated iron oxide lithium-ion-battery electrode, and preparation method and application thereof | |
| CN113285050A (en) | Li-M-X-based solid lithium battery anode and preparation method thereof | |
| CN207602682U (en) | A kind of lithium battery anode structure | |
| CN115939361A (en) | Copper phosphide-doped hard carbon composite material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20210302 Address after: No. 88, Yingbin Avenue, Shouan Town, Pujiang County, Chengdu, Sichuan 610000 Applicant after: Chengdu Dachao Technology Co.,Ltd. Address before: No. 1609, 16th floor, Hemei Begonia Center (Tianfu maker), No. 2039, south section of Tianfu Avenue, Tianfu New District, Chengdu, Sichuan 610213 Applicant before: CHENGDU YIDAO TECHNOLOGY PARTNERSHIP (L.P.) |
|
| TA01 | Transfer of patent application right | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20180601 |
|
| RJ01 | Rejection of invention patent application after publication |