CN108448094A - A kind of surface modification device of positive electrode and a kind of preparation method of positive electrode - Google Patents
A kind of surface modification device of positive electrode and a kind of preparation method of positive electrode Download PDFInfo
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- CN108448094A CN108448094A CN201810235356.1A CN201810235356A CN108448094A CN 108448094 A CN108448094 A CN 108448094A CN 201810235356 A CN201810235356 A CN 201810235356A CN 108448094 A CN108448094 A CN 108448094A
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- 230000004048 modification Effects 0.000 title claims abstract description 44
- 238000012986 modification Methods 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000000463 material Substances 0.000 claims abstract description 113
- 238000005243 fluidization Methods 0.000 claims abstract description 84
- 230000007246 mechanism Effects 0.000 claims abstract description 63
- 238000007599 discharging Methods 0.000 claims abstract description 25
- 238000000889 atomisation Methods 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 15
- 230000008569 process Effects 0.000 claims abstract description 14
- 239000011248 coating agent Substances 0.000 claims abstract description 9
- 238000000576 coating method Methods 0.000 claims abstract description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 6
- 239000005416 organic matter Substances 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- 229910021645 metal ion Inorganic materials 0.000 claims description 5
- 235000019441 ethanol Nutrition 0.000 claims description 4
- 230000008676 import Effects 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- 229910013361 LiNixCoyAl1-x-yO2 Inorganic materials 0.000 claims description 3
- 229910013421 LiNixCoyMn1-x-yO2 Inorganic materials 0.000 claims description 3
- 229910013427 LiNixCoyMn1−x−yO2 Inorganic materials 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 239000000126 substance Substances 0.000 abstract description 13
- 239000002245 particle Substances 0.000 description 14
- 239000007787 solid Substances 0.000 description 12
- 239000010405 anode material Substances 0.000 description 9
- 239000013618 particulate matter Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 6
- 229910001416 lithium ion Inorganic materials 0.000 description 6
- 230000008859 change Effects 0.000 description 5
- 238000007792 addition Methods 0.000 description 3
- 238000010835 comparative analysis Methods 0.000 description 3
- 230000005484 gravity Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000012876 topography Methods 0.000 description 3
- 229910013716 LiNi Inorganic materials 0.000 description 2
- 238000005253 cladding Methods 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000003595 mist Substances 0.000 description 2
- 238000006011 modification reaction Methods 0.000 description 2
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- 239000002699 waste material Substances 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- 229910018632 Al0.05O2 Inorganic materials 0.000 description 1
- 229910000975 Carbon steel Inorganic materials 0.000 description 1
- 229910001335 Galvanized steel Inorganic materials 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000010962 carbon steel Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
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- 229910052744 lithium Inorganic materials 0.000 description 1
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- 239000007921 spray Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
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- 238000010792 warming Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
-
- 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 invention discloses a kind of surface modification device of positive electrode, which includes fluidizing cavity and feeding mechanism, fluidization mechanism and discharging mechanism on fluidisation cavity.The invention also discloses a kind of preparation methods of the positive electrode based on above-mentioned surface modification device to include：Configure positive electrode and modified material；Positive electrode is directed into fluidizing chamber body, atomization process is carried out to the positive electrode imported by fluidization mechanism；Modified material is directed into fluidizing chamber body, so that the positive electrode that modified material is atomized in fluidizing chamber body carries out surface coating modification；The positive electrode being modified is exported out of fluidizing chamber body by discharging mechanism.The surface modification device of positive electrode provided by the invention is simple in structure, rationally distributed and easy to operate；The preparation method of positive electrode can prepare stable clad, and the specific capacity of battery is improved while not damaging the chemical property of battery.
Description
Technical field
The present invention relates to a kind of modifications of the surface of field of lithium ion battery more particularly to positive electrode of lithium ion battery
Device and a kind of preparation method of positive electrode.
Background technology
Lithium ion battery relies on the advantages that its high-energy density and long circulation life to be widely used in multiple fields,
Such as field of energy source power.Electric vehicle and energy-accumulating power station in field of energy source power is very big to the use scale of construction of lithium ion battery,
With the rapid extension of electric vehicle and energy-accumulating power station, to the performance of the following lithium ion battery, more stringent requirements are proposed, can
It is attributed to：High-energy density, high power characteristic, high safety performance, low cost and low (nothing) pollution.The performance of this " three high two is low "
It is substantially dependent on the chemical property of positive and negative pole material in battery.By taking nickelic positive electrode as an example, nickelic system's positive electrode
Actual specific capacity is well below its theoretical specific capacity.Charge cutoff voltage by improving battery helps to improve the specific volume of battery
Amount, but it is only limitted to the increase rate of a smaller charge cutoff voltage.If further increasing charge cutoff voltage to obtain
Higher reversible specific capacity can then lead to a series of the problem of seriously affecting battery performance, such as electrolyte decomposition, positive and negative
Side reaction etc. occurs for pole material surface.
As it can be seen that at least having the following defects in the prior art：Height can only be improved by a small margin by improving charge cutoff voltage
The specific capacity of nickel system positive electrode, the actual specific capacity of gained is still well below theoretical specific capacity after raising.
Therefore, it is necessary to provide a kind of technological means to solve drawbacks described above.
Invention content
It is an object of the invention to overcome the defect of the prior art, a kind of table of the positive electrode of lithium ion battery is provided
Surface modifying device and a kind of preparation method of positive electrode, it is therefore an objective to by the way that the suitable of height ratio capacity is made in surface modification device
Positive electrode for lithium battery.
The present invention provides a kind of surface modification device of positive electrode, and the surface modification device is for coating modified material
On the surface of positive electrode, including：
Fluidize cavity；
Feeding mechanism is set on fluidisation cavity, for positive electrode and modified material to be added in surface modification device；
Fluidization mechanism is set on fluidisation cavity, for disperseing positive electrode and atomization modified material, so that modified material packet
It is overlying on positive electrode；
Discharging mechanism is set on fluidisation cavity, for exporting the positive electrode being modified out of surface modification device.
Preferably, fluidisation cavity includes two front end faces being oppositely arranged, and fluidization mechanism includes inlet section and outlet section, into
Wind portion and outlet section are respectively arranged on two end faces of fluidisation cavity；Inlet section include inlet section holder and be set to inlet section holder
On wind turbine and heating component, inlet section holder connect with fluidisation cavity, wind turbine is used for toward the interior importing air-flow of fluidizing chamber body with mist
Change positive electrode, heating component is used to heat the air-flow imported in fluidizing chamber body so that positive electrode and modified material heat up；
Outlet section includes outlet section holder and the cyclone separator on the holder of outlet section, and cyclone separator is used in separation bubble
Modified positive electrode.
Preferably, feeding mechanism includes the positive electrode input unit being set on fluidizing chamber body side surface and is vertical at fluidizing chamber
The quantity of the modified material input unit in body end face, positive electrode input unit and modified material input unit is respectively more than one.
Preferably, modified material input unit is one toward the pipeline of end face extension where discharging mechanism and is set to pipeline one end
Nozzle, pipeline the other end connection fluidisation cavity；Modified material input unit it is parallel to each other be arranged in pairs and quantity is no less than
Two.
Preferably, nozzle is rotatably set on pipeline, and nozzle is equipped with several trepannings, a diameter of 0.5-3.0 of trepanning
Millimeter.
The present invention also provides a kind of preparation method of the positive electrode based on above-mentioned surface modification device, the preparation method packets
Include following steps：
(1) positive electrode and modified material are configured；
(2) positive electrode is directed into fluidizing chamber body by positive electrode input unit, by fluidization mechanism to having imported
Positive electrode carry out atomization process；
(3) modified material is directed into via nozzle in fluidizing chamber body by modified material input unit, so that modified material
The positive electrode being atomized in fluidizing chamber body carries out surface coating modification；
(4) positive electrode being modified is exported out of fluidizing chamber body by discharging mechanism.
Preferably, positive electrode includes LiNixCoyMn1-x-yO2And/or LiNixCoyAl1-x-yO2One or both of
Mixture；Modified material includes metal salt and organic matter, wherein the metal ion of metal salt is Al3+、Mg2+And/or Mn2+In
One or more, organic matter is one or more mixtures in ethyl alcohol, ethylene glycol and/or polyethylene glycol oxide.
Preferably, the addition of positive electrode and modified material is according to the metal in the nickel and modified material in positive electrode
The molar ratio of ion is 0.01~0.05:1 determines.
Preferably, the atomization temperature of the atomization process in step (2) is within 350-750 degrees Celsius, and nebulisation time is in 10-
Within 80 minutes.
Preferably, the rotary speed of the nozzle in step (3) is 300-1000 revs/min.
To sum up, a kind of surface modification device of positive electrode is used to modified material being coated on the surface of positive electrode, packet
Fluidisation cavity and feeding mechanism, fluidization mechanism and discharging mechanism on fluidisation cavity are included, feeding mechanism is used to change toward surface
Property device in positive electrode and modified material is added；Fluidization mechanism is for being atomized positive electrode so that modified material is coated on anode
On material；Discharging mechanism out of surface modification device for exporting the positive electrode being modified.
A kind of preparation method of the positive electrode based on above-mentioned surface modification device includes：Configure positive electrode and modified material
Material；Positive electrode is directed into fluidizing chamber body, atomization process is carried out to the positive electrode imported by fluidization mechanism；It will change
Property material be directed into fluidizing chamber body so that the positive electrode that is atomized in fluidizing chamber body of modified material carries out surface cladding and changes
Property；The positive electrode being modified is exported out of fluidizing chamber body by discharging mechanism.
Compared with prior art, the surface modification device of positive electrode provided by the invention it is simple in structure, it is rationally distributed and
It is easy to operate；The preparation method of positive electrode based on above-mentioned surface modification device is simple for process, production efficiency is high, can prepare
Go out stable clad, to improve the specific capacity of battery while not damaging the chemical property of battery.
Description of the drawings
Fig. 1 is a kind of structural schematic diagram of the surface modification device for positive electrode that a preferred embodiment of the present invention provides.
Fig. 2 is a kind of flow chart of the preparation method for positive electrode that a preferred embodiment of the present invention provides.
Fig. 3 is a kind of surface topography micromechanism figure of positive electrode before modified.
Fig. 4 is the surface topography micro-structure diagram after positive electrode shown in Fig. 3 is modified.
Wherein, 1, fluidisation cavity, 2, feeding mechanism, 21, positive electrode input unit, 22, modified material input unit, 221, pipe
Road, 222, nozzle, 3, fluidization mechanism, 31, inlet section, 311, inlet section holder, 312, wind turbine, 313, heating component, 32, outlet air
Portion, 321, outlet section holder, 322, cyclone separator, 4, discharging mechanism.
Specific implementation mode
Below in conjunction with attached drawing of the embodiment of the present invention, technical solution in the embodiment of the present invention carries out clearly and completely
Description, it is clear that the described embodiments are merely a part of the embodiments of the present invention, instead of all the embodiments.Based on this hair
Bright embodiment, the other embodiments that those skilled in the art are obtained without making creative work, all
Belong to the scope of protection of the invention.
Fig. 1 show a preferred embodiment of the present invention, which provides a kind of surface modification device of positive electrode, should
Surface modification device is used to modified material being coated on the surface of positive electrode, including：
Fluidize cavity 1；
Feeding mechanism 2 is set on fluidisation cavity 1, for positive electrode and modified material to be added in surface modification device；
Fluidization mechanism 3 is set on fluidisation cavity 1, for disperseing positive electrode and atomization modified material, so that modified material
It is coated on positive electrode；
Discharging mechanism 4 is set on fluidisation cavity 1, for exporting the positive electrode being modified out of surface modification device.
Specifically, fluidisation cavity 1 can be the hollow-core constructions such as cylinder, square body, cuboid, and preferably draw ratio is more than 1
Hollow cylinder；Heat-resisting steel and iron parts or other alloy components, such as carbon steel sheet, galvanized steel plain sheet, stainless steel plate etc. are selected on material.
Feeding mechanism 2 and discharging mechanism 4 are respectively positioned on the side of fluidisation cavity 1, and are in the layout of " one on the other ", in order to
The gravity for being conveniently operated and overcoming material itself, feeding mechanism 2 relative to discharging mechanism 4 above；In addition, in order to make stream
Changing has interaction of enough large spaces for modified material and positive electrode in cavity 1, feeding mechanism 2 and discharging mechanism 4 are distinguished
Set on 1 bottom end of fluidisation 1 top of cavity and fluidisation cavity.It can be arranged with for positive electrode and modified material on feeding mechanism 2
Material is first delivered to fluidizing chamber when importing above two material into the transport section and batch turning component fluidized in cavity 1
1 inside of body, then starts batch turning component so that material enters the inner space of fluidisation cavity 1；Compared to directly introducing material into
It fluidizes in cavity 1, waste of the material outside fluidisation cavity 1 can be effectively prevented from using above-mentioned feeding manner, also can guarantee material
Material can be imported smoothly.
In the present embodiment, fluidisation cavity 1 includes two front end faces being oppositely arranged, and fluidization mechanism 3 includes inlet section 31
With outlet section 32, inlet section 31 and outlet section 32 are respectively arranged on two end faces of fluidisation cavity 1；
Inlet section 31 includes inlet section holder 311 and the wind turbine 312 on inlet section holder 311 and heating component 313,
31 holder of inlet section is connect with fluidisation cavity 1, and wind turbine 312 is used in fluidisation cavity 1 import air-flow to be atomized positive electrode, adds
Hot component 313 is used to heat the air-flow imported in fluidisation cavity 1 so that positive electrode and modified material heat up；
Outlet section 32 includes outlet section holder 321 and the cyclone separator 322 on outlet section holder 321, whirlwind point
Positive electrode from device 322 for being modified in separation bubble.
Specifically, fluidization mechanism 3 is substantially a kind of special air stream components：Inlet section 31 will be for that will fluidize outside cavity 1
Air import fluidisation cavity 1 in；Outlet section 32 is used to fluidize outside the air-flow export fluidisation cavity 1 in cavity 1.Inlet section 31
It is oppositely arranged with outlet section 32, inlet section 31 is relative to outlet section 32 in lower section.Assuming that fluidisation cavity 1 is the cylinder of a rule
Structure, inlet section 31 and the axis of straight line and cylinder where outlet section 32 do not repeat, this is primarily to prevent from not filling
Divide modified positive electrode or the positive electrode and modified material that are modified not yet that air-flow is followed directly to be flowed from outlet section 32
Go out to outside fluidisation cavity 1, causes the waste of material.Relatively stagger setting advantageously reduces material with outlet section 32 for inlet section 31
Loss, improve production efficiency.
312 preferred air blower of wind turbine in inlet section 31, the optional centrifugal impeller of impeller or axial wheel of air blower.
It should be noted that distinguish impeller, can according to flow direction of the air-flow in impeller come judge centrifugal impeller or
Axial wheel, but centrifugal impeller can also make axis outflow wind by housing design, for example, the stream in air-flow sets up one
Turnover on direction, then by that can also become and enter the wind the direction outlet air of direction level after round fluidisation cavity water conservancy diversion, this
When centrifugal impeller be particularly referred to as pipeline centrifugal blower, from the point of view of inlet and outlet direction, the pipeline centrifugal blower and traditional axis stream
The effect of impeller is the same；About the blade quantity of impeller, blade quantity depends on the air pressure air flow of actual needs, general next
Say, after blade is more, and air pressure air flow is higher, but the quantity of blade increases to certain value, air pressure air flow with blade quantity variation
With regard to unobvious, here it is considered that practical air pressure air flow and the needs being used cooperatively, preferred blade quantity is no more than 20.
313 optional thermal resistance of heating component.The type of drive of wind turbine 312 and heating component 313 in the present embodiment is preferred
Electric drive, wind turbine 312 and heating component 313 together constitute a simple and practicable electric heating air blower.
A kind of equipment of the cyclone separator 322 for the separation of gas-solid system or liquid-solid system, its working principle is that leaning on
Rotary motion caused by air-flow is introduced tangentially into makes that there is the solid particle of larger centrifugal inertial force or drop to get rid of to outside wall surface point
It opens.In the present embodiment, the positive electrode being modified is suspended in the air-flow of the importing of inlet section 31, using cyclone separator 322
By positive electrode, sub-argument comes out from gas, and positive electrode drops to the fluidisation of 4 position of discharging mechanism under the effect of gravity
On the end face of cavity 1, gas then flows out outside fluidisation cavity 1.
In the present embodiment, feeding mechanism 2 includes the positive electrode input unit 21 being set on fluidisation cavity 1 side and vertical
Modified material input unit 22 set on 1 end face of fluidisation cavity, the quantity of positive electrode input unit 21 and modified material input unit 22
Respectively more than one.
Specifically, positive electrode is solid particulate matter, and modified material is solution, if solid particulate matter and solution are mixed in
Together, solid particulate matter can be agglomerated into block structure, and solution can not cmpletely infiltrate or even touch solid particulate matter, this
Just directly result in insufficient cladding of the modified material on positive electrode.In order to enable solid particulate matter fully dispersed can be opened
Come, by positive electrode and modified material respectively from the different channel of positive electrode input unit 21 and modified material input unit 22 two
Into in fluidisation cavity 1.After solid particulate matter enters fluidisation cavity 1, the wind turbine 312 of inlet section 31 imports in fluidisation cavity 1
Air-flow solid particulate matter can be raised, under the conduction of heat of thermal current, solid particulate matter can be warming up to preset temperature, should
Preset temperature is the temperature that modified material generates coating function with positive electrode；Later, modified material is inputted by modified material
Portion 22 is with atomised form and solid particulate matter haptoreaction.
Positive electrode input unit 21 is in the side of fluidisation cavity 1, anode of the modified material input unit 22 in fluidisation cavity 1
Face, this is primarily to easy to operate；The quantity of positive electrode input unit 21 and modified material input unit 22 can be one with
On, this is primarily to enable positive electrode to be come into full contact with modified material, in the formation complete packet on positive electrode surface
Coating.
In the present embodiment, modified material input unit 22 be one toward 4 place end face of discharging mechanism extend pipeline 221 and
Nozzle 222 set on 221 one end of pipeline, the other end connection fluidisation cavity 1 of pipeline 221；Modified material input unit 22 is mutually equal
It is capable to be arranged in pairs and quantity is no less than two.
Specifically, modified material input unit 22 is equivalent to a small-sized atomising mechanism.Atomization is to enter liquid injection
It in gas medium, is allowed to disperse and be fragmented into the process of little particle drop, is to be here by the abundant fragmentation of the modified material of liquid
Droplet.
It should be noted that the length toward the pipeline 221 of 4 place end face of discharging mechanism extension should be 1 height of fluidisation cavity
1/2-4/5.The air inlet flow of inlet section 31 is one of the key factor of length for determining pipeline 221.In practical application, anode
Material is toward the bottom movement of fluidisation cavity 1 under its own gravity, and at this moment modified material will be close to the bottom of fluidisation cavity 1
Portion；If the air-flow of inlet section 31 is enough big, the top of positive electrode toward fluidisation cavity 1 is raised, at this moment modified material is with regard to corresponding
Ground should appear in the top of fluidisation cavity 1.
In the present embodiment, nozzle 222 is rotatably set on pipeline 221, and nozzle 222 is equipped with several trepannings, trepanning
A diameter of 0.5-3.0 millimeters.
Specifically, the performance of nozzle 222 directly affects on the spray pattern of modified material, especially nozzle 222
The shape and size of trepanning.The smaller micro- taper hole type of the preferred diameter of trepanning on nozzle 222, micro- taper hole type can drive fluid to produce
Raw one-way flow is conducive to modified material atomization be particle is small and is evenly distributed drop.It is noted that nozzle 222
Rotating speed, jet length, that is, modified material driving source be applied to pressure on modified material solution etc. and mist droplet particle size can be produced
It is raw to influence.
Fig. 2 show a preferred embodiment of the present invention, the embodiment provide it is a kind of based on above-mentioned surface modification device just
The preparation method of pole material, the preparation method include the following steps：
(1) positive electrode and modified material are configured；
(2) positive electrode is directed into fluidisation cavity 1 by positive electrode input unit 21, by fluidization mechanism 3 to
The positive electrode of importing carries out atomization process；
(3) modified material is directed into via nozzle 222 in fluidisation cavity 1 by modified material input unit 22, so as to change
Property material positive electrode for being atomized in fluidisation cavity 1 carry out surface coating modification；
(4) positive electrode being modified is exported out of fluidisation cavity 1 by discharging mechanism 4.
In the present embodiment, positive electrode includes LiNixCoyMn1-x-yO2And/or LiNixCoyAl1-x-yO2In one kind or
Two kinds of mixture；Modified material includes metal salt and organic matter, wherein the metal ion of metal salt is Al3+、Mg2+And/or
Mn2+In it is one or more, organic matter be ethyl alcohol, ethylene glycol and/or polyethylene glycol oxide in one or more mixtures.
In the present embodiment, the addition of positive electrode and modified material is according in the nickel and modified material in positive electrode
Metal ion molar ratio be 0.01~0.05:1 determines.
In the present embodiment, the atomization temperature of the atomization process in step (2) is within 350-750 degrees Celsius, when atomization
Between within 10-80 minutes.
In the present embodiment, the rotary speed of the nozzle 222 in step (3) is 300-1000 revs/min.
In addition, in order to evaluate the performance of the positive electrode using the modification obtained by above-mentioned preparation method, using scanning electricity
Mirror observes the surface microscopic topographic for the positive electrode particle being modified, using specific surface area particle size instrument positive electrode
The grain size of particle, detect the electric property of modified positive electrode into, and after comparative analysis before modified positive electrode electrochemistry
Performance.Chemical property passes through the acid-base value Ph values of particle surface, 0.2 times of specific capacity, cycle starting specific capacity, 300 specific volumes
Amount and special capacity fade rate carry out embodiments.
Operating process in a manner of specific embodiment to above-mentioned preparation method below and related process parameters carry out detailed
Explanation is enumerated on ground.
Specific embodiment one
(1) by 1.69 grams of MgSO4·H2O, 10 grams of ethylene glycol and 190 grams of deionized waters are configured to 0.05 mole every liter and change
Property material solution；
(2) 3 to 400 degrees Celsius of fluidization mechanism is heated；
(3) 96 grams of LiNi are imported in fluidisation cavity 1 by positive electrode input unit 210.8Co0.15Al0.05O2Positive material
Material；
(4) after positive electrode is fully dispersed, modified material solution is sprayed in the powder flow of positive electrode, coating modification
Reaction time is 20 minutes, and modified anode material is made；
(5) modified anode material made from step (4) is exported from discharging mechanism 4, using scanning electron microscope and specific surface area
Particle size analyzer characterizes the basic performance of modified anode material, and is detected to the electric property of modified positive electrode.
The chemical property of positive electrode after comparative analysis before modified, corresponding specific embodiment one, the modified anode material
It is denoted as sample 1#, positive electrode before modified is denoted as 1∑#.Table 1 show sample 1#With sample 1∑#Chemical property.
1 sample 1 of table#With sample 1∑#Chemical property
As known from Table 1, after surface-modified, the surface pH value of positive electrode has dropped 0.5,0.2C capacity and has dropped
3mAh/g, cycle initial capacity improve 3mAh/g, and 300 weeks capacity improve 9mAh/g, and capacity attenuation rate has dropped 3.3%.
Therefore, modified positive electrode has more preferably chemical property.
Specific embodiment two
(1) by 3.75 grams of Al (NO3)3·9H2O, 10 grams of ethyl alcohol and 190 grams of deionized waters are configured to 0.05 mole every liter
Modified material solution；
(2) 3 to 350 degrees Celsius of fluidization mechanism is heated；
(3) 97 grams of LiNi are imported in fluidisation cavity 1 by positive electrode input unit 210.8Mn0.1Co0.1O2Positive electrode；
(4) after positive electrode is fully dispersed, modified material solution is sprayed in the powder flow of positive electrode, coating modification
Reaction time is 20 minutes, and modified anode material is made；
(5) modified anode material made from step (4) is exported from discharging mechanism 4, using scanning electron microscope and specific surface area
Particle size analyzer characterizes the basic performance of modified anode material, and is detected to the electric property of modified positive electrode.
The chemical property of positive electrode after comparative analysis before modified, corresponding specific embodiment two, the modified anode material
It is denoted as sample 2#, positive electrode before modified is denoted as 2∑#.Table 1 show sample 2#With sample 2∑#Chemical property.
2 sample 2 of table#With sample 2∑#Chemical property
As known from Table 2, after surface-modified, the surface pH value of positive electrode has dropped 0.4,0.2C capacity and has dropped
2mAh/g, cycle initial capacity improve 5mAh/g, and 300 weeks capacity improve 10mAh/g, and capacity attenuation rate has dropped 2.7%.
Therefore, modified positive electrode has more preferably chemical property.
Performance in order to further illustrate modified positive electrode is better, below to the sample in specific embodiment two
2#With sample 2∑#Topography scan figure and specific surface area analyzed.It is respectively sample 2 shown in Fig. 3 and Fig. 4#With sample 2∑#'s
Microscopic appearance figure.It can be seen that the particle surface of modified positive electrode becomes coarse, it can be seen that, modified material is
Clad is formed in particle surface.Table 3 show sample 2#With sample 2∑#Specific surface area.As known from Table 3, modified sample 2#
Specific surface area value improve, illustrate one layer of coarse clad of surface travel, it is modified simultaneously to increase specific surface area
The grain size of positive electrode particle increases afterwards, and this also illustrates modified materials to have coated positive electrode particle.
3 sample 2 of table#With sample 2∑#Specific surface area
To sum up, a kind of surface modification device of positive electrode is used to modified material being coated on the surface of positive electrode, packet
Fluidisation cavity 1 and feeding mechanism 2, fluidization mechanism 3 and discharging mechanism 4 on fluidisation cavity 1 are included, feeding mechanism 2 is for past
Positive electrode and modified material are added in surface modification device；Fluidization mechanism 3 is for being atomized positive electrode so that modified material packet
It is overlying on positive electrode；Discharging mechanism 4 out of surface modification device for exporting the positive electrode being modified.
A kind of preparation method of the positive electrode based on above-mentioned surface modification device includes：Configure positive electrode and modified material
Material；Positive electrode is directed into fluidisation cavity 1, atomization process is carried out to the positive electrode imported by fluidization mechanism 3；It will
Modified material is directed into fluidisation cavity 1, so that the positive electrode that modified material is atomized in fluidisation cavity 1 carries out surface packet
Cover modification；The positive electrode being modified is exported from fluidisation cavity 1 is interior by discharging mechanism 4.
Compared with prior art, the surface modification device of positive electrode provided by the invention it is simple in structure, it is rationally distributed and
It is easy to operate；The preparation method of positive electrode based on above-mentioned surface modification device is simple for process, production efficiency is high, can prepare
Go out stable clad, to improve the specific capacity of battery while not damaging the chemical property of battery.
Above content is only citing made for the present invention and explanation, affiliated those skilled in the art are to being retouched
The specific embodiment stated is done various modifications or additions or is substituted using similar method, without departing from invention or is surpassed
More range defined in present claims, is within the scope of protection of the invention.
Claims (10)
1. a kind of surface modification device of positive electrode, the surface for modified material to be coated on to positive electrode, feature exist
In, including：
Fluidize cavity；
Feeding mechanism is set on the fluidisation cavity, for positive electrode and modified material to be added in the surface modification device
Material；
Fluidization mechanism is set on the fluidisation cavity, for disperseing positive electrode and atomization modified material, so that modified material packet
It is overlying on positive electrode；
Discharging mechanism is set on the fluidisation cavity, for exporting the positive electrode being modified out of described surface modification device.
2. surface modification device according to claim 1, which is characterized in that the fluidisation cavity is oppositely arranged including two
Front end face, the fluidization mechanism includes inlet section and outlet section, and the inlet section and the outlet section are respectively arranged on the stream
On two end faces for changing cavity；
The inlet section includes inlet section holder and the wind turbine on the inlet section holder and heating component, the inlet section
Holder is connect with the fluidisation cavity, and the wind turbine is used for toward the interior air-flow that imports of the fluidizing chamber body to be atomized positive electrode, institute
Heating component is stated for heating the air-flow imported in the fluidizing chamber body so that positive electrode and modified material heat up；
The outlet section includes outlet section holder and the cyclone separator on the outlet section holder, the cyclone separator
Positive electrode for being modified in separation bubble.
3. surface modification device according to claim 1, which is characterized in that the feeding mechanism includes being set to the fluidisation
Positive electrode input unit on cavity side and the modified material input unit for being vertical at fluidizing chamber body end face, the anode
The quantity of material input unit and the modified material input unit is respectively more than one.
4. surface modification device according to claim 3, which is characterized in that the modified material input unit is one described in
The pipeline that end face where discharging mechanism extends and the nozzle set on described pipeline one end, described in the other end connection of the pipeline
Fluidize cavity；
The modified material input unit it is parallel to each other be arranged in pairs and quantity is no less than two.
5. surface modification device according to claim 4, which is characterized in that the nozzle is rotatably set to the pipeline
On, the nozzle be equipped with several trepannings, a diameter of 0.5-3.0 millimeters of the trepanning.
6. a kind of preparation method of positive electrode, the preparation method based on the surface modification device described in claim 1 to 5,
It is characterised in that it includes following steps：
(1) positive electrode and modified material are configured；
(2) positive electrode is directed into the fluidizing chamber body by the positive electrode input unit, passes through the fluidization mechanism
Atomization process is carried out to the positive electrode imported；
(3) modified material is directed into via the nozzle in the fluidizing chamber body by the modified material input unit, so that
The positive electrode that modified material is atomized in the fluidizing chamber body carries out surface coating modification；
(4) positive electrode being modified is exported out of described fluidizing chamber body by the discharging mechanism.
7. preparation method according to claim 6, which is characterized in that positive electrode includes LiNixCoyMn1-x-yO2And/or
LiNixCoyAl1-x-yO2One or both of mixture；
Modified material includes metal salt and organic matter, wherein the metal ion of metal salt is Al3+、Mg2+And/or Mn2+In one
Kind is a variety of, and organic matter is one or more mixtures in ethyl alcohol, ethylene glycol and/or polyethylene glycol oxide.
8. preparation method according to claim 6, which is characterized in that the addition of positive electrode and modified material is according to just
The molar ratio of the metal ion in nickel and modified material in the material of pole is 0.01~0.05:1 determines.
9. preparation method according to claim 6, which is characterized in that the atomization temperature of the atomization process in step (2) exists
Within 350-750 degrees Celsius, nebulisation time is within 10-80 minutes.
10. preparation method according to claim 6, which is characterized in that the rotary speed of the nozzle in step (3) is
300-1000 revs/min.
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