CN109647293A - A kind of system and method for anode material for lithium-ion batteries metal oxide coating modification - Google Patents
A kind of system and method for anode material for lithium-ion batteries metal oxide coating modification Download PDFInfo
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Abstract
The present invention relates to a kind of system and method for anode material for lithium-ion batteries metal oxide coating modification, the system mainly includes that feed bin, screw-feeder, inlet valve, fluidized-bed reactor, outlet valve, reactor product cooler, product collector, burner, reaction carrier gas preheater, reaction raw materials generator, reaction raw materials nozzle, fluidized carrier gas preheater, primary cyclone, secondary cyclone, bagroom and hydrochloric acid tail gas absorption device are formed according to given combinations；The method is the metal oxide coating modification method based on the system, obtains metal oxide clad anode composite granule by fluidization chemical vapor deposition.The present invention has many advantages, such as that coating efficiency is high, simple process is controllable, at low cost, is suitble to the scale industrial production of lithium ion battery metal oxide coating modification positive electrode, with good economic efficiency and social benefit.
Description
Technical field
The invention belongs to lithium ion battery materials, chemical field, and in particular to a kind of anode material for lithium-ion batteries metal
The system and method for oxide coating modification.
Background technique
In recent years, with the fast development of new-energy automobile, people propose the performance of lithium-ion-power cell higher
Requirement.Core component of the electrode material as lithium ion battery, decides the performance of lithium ion battery.It is opposite to develop into
Ripe stable commercial graphite cathode, the positive electrode research and development for being directed to high capacity, long-life, low cost and safety and environmental protection seem outstanding
It is urgent.Commercial anode material for lithium-ion batteries at present, mainly there is cobalt acid lithium, the ternary material, spinelle knot of layer structure
The LiMn2O4 of structure and the LiFePO4 of olivine structural.Wherein ternary material specific capacity with higher, energy density and function
Rate density.However the chemical property of ternary material, thermal stability and structural stability still need to further increase, especially in height
Under temperature and high power amplifier (being higher than 4.2V) environment.With the raising of nickel content, these problems seem especially prominent, serious to limit
The development and application of material are made.
Metal oxide cladding is a kind of highly effective feasible method for solving the problems, such as this, can by metal oxide cladding
To be contacted as protective layer isolation electrolyte with the direct of positive electrode, related side effect is reduced, the analysis of transition metal is such as reduced
Out, thinner SEI film, the precipitation for reducing oxygen atom etc. are formed, to improve the electrochemical stability of material.In addition selection is suitable
Covering material, electron conduction, ionic conductivity and the thermal stability of material are also available to be improved significantly.Therefore, golden
It is significant to the performance improvement of anode material for lithium-ion batteries to belong to oxide coating modification.
Currently, the metal oxide method for coating of anode material for lithium-ion batteries is broadly divided into two major classes, it is liquid phase respectively
Mixing combines sintering and mechanical ball mill mixing method.
(1) liquid phase mixing combines sintering: it is the metal oxide cladding side of most mainstream that liquid phase mixing, which combines heat treatment method,
Method, in particular to positive electrode and liquid solution containing metal front are mixed, prepares metal oxide cladding through Overheating Treatment
Material.The patent CN101510606B of Beijing University of Chemical Technology mixes the salting liquid of aluminium with the suspension of lithium manganate having spinel structure,
It is obtained through suspension dry (constant temperature 6~24 hours at 50~150 DEG C) and heat treatment (constant temperature 5~15 hours at 300~600 DEG C)
Alumina-coated manganate cathode material for lithium.The patent CN103178258B of Ningde Amperex Technology Co., Ltd. is by by lithium nickel cobalt
Manganese oxygen presoma, water-soluble aluminum salt and equal powder liquid phase mix, and are heat-treated and are aoxidized at 400~600 DEG C after filtration drying
Aluminium coats ternary material.Titanium-containing compound is distributed to dispersion by the patent CN103441267A of Ocell New Energy Technology Co., Ltd.
In agent, cobalt acid lithium powder is added, the lithium cobaltate cathode material of coated by titanium dioxide is obtained after mixing, drying and roasting.It
The patent CN103985863A of saliva university is auxiliary using the sol-gel method and polyvinyl alcohol of control pH value using cerous nitrate as raw material
The suspension mixing method helped prepares cerium oxide coated LiFePO 4 for lithium ion batteries positive electrode.The patent CN102637871A of Central South University is by vanadium source
It is dissolved in medium and forms solution, be subsequently added into positive electrode, obtain the anode of vanadic anhydride cladding through dry and high temperature sintering
Material, wherein the high temperature sintering time is up to 10~32 hours.The patent CN101834289B of Dongguan New Energy Technology Co
Zirconium salt solution is mixed with positive electrode, it is dry at 60~200 DEG C and 800~1000 DEG C at roast, form surface cladding two
The positive electrode of zirconium oxide.Wuxi star wave energy source Science and Technology Ltd. (CN104577128A), Liaoming Petrochemical Univ
(CN102244260A), Southern Yangtze University (CN104134795A), University of Fuzhou (CN106252641A), Wuxi spar new energy
Co., Ltd (CN107275619A) and Xinxiang University (CN108336348A) patent that also disclose technique similar.In order to make to burn
Tie it is more thorough, form stable clad, these patents all use (200~500 DEG C) of preheating combinations in low temperature (600~
1000 DEG C) heat treatment, pyrolysis time is generally up to 12~24 hours, or even is had 32 hours.Liquid phase mixing combines sintering process band
Filtration of material, washing and the sintering process complex process come, the processing time is tediously long, will cause the liter of production efficiency reduction and cost
It is high.The problem of simultaneous oxide forming process is from forming core also influences metal oxide cladding and changes to chemical property
Kind effect, performance boost effect are still to be improved.
(2) mechanical ball mill mixes: other than liquid phase mixes and combines sintering, also having partial monopoly to mix using mechanical ball mill
Method.The patent CN104701532A of Jiangsu Kejie Lithium Battery Co., Ltd. discloses a kind of nano aluminium oxide solid phase cladding
Directly ball mill is added in cobalt acid lithium and Nano-sized Alumina Powder by method, carries out mechanical ball mill with the abrading-ball of twice of quality of material
Mixing.The patent CN103390748B of Ou Sai new energy Science and Technology Co., Ltd. disclose it is a kind of using mechanical ball mill directly will
Cobalt acid lithium and aluminum contained compound mixing, mixture are heated to obtain the lithium cobaltate cathode material of alumina-coated again.It closes
High oxide and positive electrode are carried out 2~10 hours abundant ball milling mixings by the patent CN103996832A of fertile polytechnical university
Prepare metallic oxide cladded anode material.The patent CN102280639B of Chinese Academy Of Sciences Process Engineering Research Institute is then by mistake
Cross metal oxide and LiFePO 4 material mixing and ball milling 12~24 hours.Although the method preparation process of mechanical ball mill mixing
Simply, at low cost, but the operating time is long, it is uneven to mix, and metal oxide and positive electrode insufficient contact, is often in
Existing (metal oxide) particle point contact, covered effect is not good enough, and material property improves extremely limited.
Other than above two main metal oxide method for coating, also there are a few patents using chemical vapor deposition
Method.The patent CN104201323B of Shanghai University Of Electric Power prepares alumina-coated cobalt acid lithium using chemical vapor deposition method
The uniformity of positive electrode, cladding is significantly improved.But basic operation technique is also more complicated, is specifically divided into three steps,
The first step is to heat aluminum contained compound and the mixture of cobalt acid lithium, keeps the temperature 0.5~2 hour at 130~350 DEG C, and gasify aluminium
Compound；Second step is to be passed through vapor, and reaction generates aluminium hydroxide and is deposited on cobalt acid lithium surface, is reacted 0.5~2 hour；The
Three steps are sintering, are warming up to 300~700 DEG C, keep the temperature 2~9 hours.Vapor deposition is in the metal oxide cladding side of particle surface
Method has apparent performance advantage compared to aforementioned two ways, still, the skill of current vapor deposition coated metal oxide
Art is carried out in converter or the fixed reaction bed of tradition.The structure design of converter influences covered effect at obvious, anode
Material powder particle rolls in the reactor, and particle surface is exposed limited, so that it cannot realize comprehensive cladding of powder surface.
Meanwhile converter vapor deposition can not really realize continuous production, cause deposition higher cost.By the way of powder tiling, no
Foot place mainly has two o'clock, first is that the powder of tiling only has exposed surface portion deposition efficiency high, and non-exposed part deposits
Low efficiency, for powder, when covering amount is larger, deposition uniformity will be deteriorated；Second is that fixed reaction bed tiling powder
Mode cause single cladding process handle powder it is less, yield is lower, and can not continuous production, seriously hinder vapor deposition
The application of coating technology.
Fluidized-bed chemical vapor deposition technology combines chemical vapor deposition and fluidization technology, is a kind of novel material
Technology of preparing is, it can be achieved that high efficiency, low cost coating modification and continuous production.In a fluidized bed, particle is under airflow function in stream
State, gas reactant carrier band by way of enter fluidized bed, chemically reacted in high-temperature region, formation superfines or
It is deposited on particle surface.The initial application of the technology is nuclear fuel field, is mainly used to application and preparation in high temperature gas cooled reactor
Coated fuel particles (CN204865735U, CN105139897A, CN103357869B and CN102231291A etc.), it is subsequent gradually
Expand to carbon nanotube preparation, polysilicon preparation, catalytic carrier and the fields such as powder-modified.
The effect of metal oxide cladding directly affects the chemical property of positive electrode, summarizes existing positive electrode metal
The mixing of oxide coating technology, either liquid phase combines sintering, mechanical ball mill mixing or conventional chemical vapor deposition, can not
Realize that efficiently controllable metal oxide coats continuous production.Therefore, this field needs a kind of high-efficiency and economic, is suitble to scale metaplasia
The metal oxide coating technology of production.
Summary of the invention
The purpose of the present invention is to provide a kind of precisely cladding, good economy performance, it is easy to operate, suitable for continuous large-scale production
The system and method for metallic oxide cladded anode material is based on fluidized-bed chemical vapor deposition technology.
To reach this purpose, the specific technical solution of the present invention is as follows:
The present invention provides a kind of system of anode material for lithium-ion batteries metal oxide coating modification, the system comprises
Feed bin 1, screw-feeder 2, inlet valve 3, fluidized-bed reactor 4, outlet valve 5, reactor product cooler 6, product collector 7, burning
Device 8, reaction carrier gas preheater 9, reaction raw materials generator 10, reaction raw materials nozzle 11, fluidized carrier gas preheater 12, one cyclonic
Separator 13, secondary cyclone 14, bagroom 15 and hydrochloric acid tail gas absorption device 16；
The discharge port of the feed bin 1 is connected with the feed inlet of screw-feeder 2, the discharge port of the screw-feeder 2
It is connected with the feed inlet of inlet valve 3, the discharge port of the inlet valve 3 is connected with the feed inlet of fluidized-bed reactor 4, described
The air inlet of fluidized-bed reactor 4 is connected with the gas outlet of fluidized carrier gas preheater 12；The air inlet of the fluidized-bed reactor 4
Mouth is connected with the gas outlet of reaction raw materials nozzle 11, the air inlet of reaction raw materials nozzle 11 and going out for reaction raw materials generator 10
Port is connected, and the air inlet of reaction raw materials generator 10 is connected with the gas outlet for reacting carrier gas preheater 9, the fluidized bed
The discharge port of reactor 4 is connected with the feed inlet of inlet valve 5, the feed inlet phase of the discharge port and reactor product cooler 6 of inlet valve 5
Connection, the discharge port of reactor product cooler 6 are connected with the feed inlet of product collector 7；The gas outlet of fluidized-bed reactor 4 and one
The air inlet of grade cyclone separator 13 is connected, the gas outlet of primary cyclone 13 and the air inlet of secondary cyclone 14
Mouth is connected, the feed inlet phase of the discharge port and fluidized-bed reactor 4 of primary cyclone 13 and secondary cyclone 14
Connection, the gas outlet of secondary cyclone 14 are connected with the air inlet of bagroom 15, the discharging of bagroom 15
Mouth is connected with the feed inlet of fluidized-bed reactor 4, the gas outlet of bagroom 15 and the air inlet of hydrochloric acid tail gas absorption device 16
Mouth is connected；The gas outlet of burner 8 is connected with the air inlet for reacting carrier gas preheater 9 and fluidized carrier gas preheater 12.
A kind of method of anode material for lithium-ion batteries metal oxide coating modification of the present invention, including following step
It is rapid:
1) positive electrode powder is stopped centainly through screw-feeder 2 and inlet valve 3 into fluidized-bed reactor 4 by feed bin 1
Time returns to fluidized-bed reactor after the collection of primary cyclone 13, secondary cyclone 14 and bagroom 15
4；
2) coal gas is exchanged heat after the heating of burner 8 by reaction carrier gas preheater 9 and fluidized carrier gas preheater 12, in advance
The gas of hot gas, discharge is directly discharged with exhaust gas；Carrier gas and water are sent into fluidized carrier gas preheater 12 together and are preheated, preheating
Mixed gas afterwards, which enters fluidized-bed reactor 4, makes positive electrode powder maintain fluidization；The reacted carrier gas of another way carrier gas is pre-
Hot device 9 enters reaction raw materials generator 10 after preheating and heats reaction raw materials, the reacted raw material nozzles together with reaction raw materials steam
11 enter fluidized-bed reactor 4；Vapor deposition reaction, metal oxide deposition occur for mixed gas in fluidized-bed reactor 4
It is coated on powder surface, after the discharge of the discharge port of fluidized-bed reactor 4, is carried out through the entrance reactor product cooler 6 of outlet valve 5 cold
But, product collector 7 is entered after cooling；Reaction end gas is discharged from the gas outlet of fluidized-bed reactor 4 again, sequentially enters level-one rotation
Wind separator 13, secondary cyclone 14 and bagroom 15, from the gas outlet of bagroom 15 after separation is gathered dust
Discharge carries out absorption processing into hydrochloric acid tail gas absorption device 16, forms byproduct, and exhaust gas is expelled directly out.
Preferably, the positive electrode be ternary nickle cobalt lithium manganate, ternary nickel cobalt lithium aluminate, lithium-rich manganese-based, ferric metasilicate lithium,
One of LiFePO4, cobalt acid lithium and LiMn2O4.
Preferably, the metal oxide is aluminum oxide, titanium dioxide, zirconium dioxide, cerium sesquioxide, three oxidations
One of two lanthanums and vanadic anhydride, the mass percent of the metal oxide of cladding are 0.05~3%.
Preferably, the reaction raw materials and the metal oxide of cladding have corresponding relationship, corresponding aluminum oxide, reaction
Raw material is one of trimethyl aluminium, a Chlorodimethyl aluminium and alchlor；Corresponding titanium dioxide, reaction raw materials are titanium tetrachlorides
One of with tetraisopropyl titanate；Corresponding zirconium dioxide, reaction raw materials are four (dimethylamino) zirconiums, n-butoxy zirconium and four
One of zirconium chloride；Corresponding cerium sesquioxide, reaction raw materials are that three (isopropylcyclopentadienes) change cerium；Corresponding three oxidation two
Lanthanum, reaction raw materials are three (isopropylcyclopentadienyl) lanthanums；Corresponding vanadic anhydride, reaction raw materials are Triisopropoxyvanadium(V) oxides.
Preferably, it is former to enter the heating reaction of reaction raw materials generator 10 for the reacted carrier gas preheater 9 of the carrier gas after preheating
Material, the carrier gas is the combination of one of nitrogen, helium, argon gas, neon or at least two, by reacting carrier gas preheater 9
Carrier gas temperature afterwards is 120~300 DEG C.
Preferably, the carrier gas forms gaseous mixture with vapor and enters fluidized bed after the preheating of fluidized carrier gas preheater 12
Reactor 4 is hydrolyzed by reaction raw materials gas phase, in positive electrode powder granule surface depositing metal oxide, the gas phase water
It is 1:2~1:17 that solution preocess, which is passed through vapor and the mass ratio of reaction raw materials, and reaction temperature is 200~600 DEG C, and material powder exists
Residence time in fluidized-bed reactor 4 is 4~30 minutes.
The method of positive electrode metal oxide cladding provided by the invention, coats skill compared to existing metal oxide
Art, present invention has an advantage that
(1) the metal oxide clad of in-situ deposition, content is controllable, is uniformly completely coated on positive electrode surface, mentions
Rise the significant effect of positive electrode chemical property.
(2) fluidized bed plant and method can make positive electrode powder uniformly quick particulate fluidization, and fine powder difficulty is overcome to fluidize
The shortcomings that；Vapor deposition reaction carries out in a fluidized bed, and gas-solid contact is abundant, and reaction efficiency is high, and the reaction time is short；Reactor beds
Type is simple, easily controllable and amplification.Each device of system belongs to chemical industry routine model specification, is not necessarily to specific customization；With nothing
The advantages that pollutant effluents discharge, production energy consumption and operating cost are low, stable product quality, is suitable for high-test metal oxide packet
The large-scale production of coated positive pole material has good economic and social benefit.
Detailed description of the invention
Fig. 1 is positive electrode metal oxide encasing system process flow diagram provided by the invention；
Fig. 2 is the scanning of the aluminum oxide cladding ternary nickel-cobalt lithium manganate material particle of embodiment 3 provided by the invention
Electron micrograph；
Fig. 3 is the scanning electricity of the coated by titanium dioxide ternary nickel-cobalt lithium manganate material particle of embodiment 4 provided by the invention
Sub- microscope photo；
Appended drawing reference:
1, feed bin；2, screw-feeder；3, inlet valve；4, fluidized-bed reactor；5, outlet valve；6, reactor product cooler；7,
Product collector；8, burner；9, carrier gas preheater is reacted；10, reaction raw materials generator；11, reaction raw materials nozzle；12, it flows
Change carrier gas preheater；13, primary cyclone；14, secondary cyclone；15, bagroom；16, hydrochloric acid tail gas is inhaled
Receive device.
Specific embodiment
To make the object, technical solutions and advantages of the present invention clearer, below in conjunction with attached drawing of the invention, to this hair
Technical solution in bright embodiment carries out clear and complete description, but is not limited to protection scope of the present invention:
Embodiment 1
A kind of system of anode material for lithium-ion batteries metal oxide coating modification
As shown in Figure 1, the system comprises sequentially connected feed bin 1, screw-feeder 2, inlet valves 3, fluidized-bed reaction
Device 4, outlet valve 5, reactor product cooler 6, product collector 7, burner 8, reaction carrier gas preheater 9, reaction raw materials generator 10,
Reaction raw materials nozzle 11, fluidized carrier gas preheater 12, primary cyclone 13, secondary cyclone 14, bagroom
15 and hydrochloric acid tail gas absorption device 16；
The discharge port of the feed bin 1 is connected with the feed inlet of screw-feeder 2, the discharge port of the screw-feeder 2
It is connected with the feed inlet of inlet valve 3, the discharge port of the inlet valve 3 is connected with the feed inlet of fluidized-bed reactor 4, described
The air inlet of fluidized-bed reactor 4 is connected with the gas outlet of fluidized carrier gas preheater 12；The air inlet of the fluidized-bed reactor 4
Mouth is connected with the gas outlet of reaction raw materials nozzle 11, the air inlet of reaction raw materials nozzle 11 and going out for reaction raw materials generator 10
Port is connected, and the air inlet of reaction raw materials generator 10 is connected with the gas outlet for reacting carrier gas preheater 9, the fluidized bed
The discharge port of reactor 4 is connected with the feed inlet of inlet valve 5, the feed inlet phase of the discharge port and reactor product cooler 6 of inlet valve 5
Connection, the discharge port of reactor product cooler 6 are connected with the feed inlet of product collector 7；The gas outlet of fluidized-bed reactor 4 and one
The air inlet of grade cyclone separator 13 is connected, the gas outlet of primary cyclone 13 and the air inlet of secondary cyclone 14
Mouth is connected, the feed inlet phase of the discharge port and fluidized-bed reactor 4 of primary cyclone 13 and secondary cyclone 14
Connection, the gas outlet of secondary cyclone 14 are connected with the air inlet of bagroom 15, the discharging of bagroom 15
Mouth is connected with the feed inlet of fluidized-bed reactor 4, the gas outlet of bagroom 15 and the air inlet of hydrochloric acid tail gas absorption device 16
Mouth is connected；The gas outlet of burner 8 is connected with the air inlet for reacting carrier gas preheater 9 and fluidized carrier gas preheater 12.
Embodiment 2
A kind of method of anode material for lithium-ion batteries metal oxide coating modification:
The method of the metal oxide coating modification, include the following steps: positive electrode powder by feed bin 1 through spiral into
Glassware 2 and inlet valve 3 enter fluidized-bed reactor 4 and stop certain time, through primary cyclone 13, secondary cyclone
14 and bagroom 15 collect after return to fluidized-bed reactor 4；After the discharge of the discharge port of fluidized-bed reactor 4, through discharging
Valve 5 is cooled down into reactor product cooler 6, enters product collector 7 after cooling；
Coal gas is exchanged heat after the heating of burner 8 by reaction carrier gas preheater 9 and fluidized carrier gas preheater 12, is preheated
The gas of gas, discharge is directly discharged with exhaust gas；Carrier gas and water are sent into fluidized carrier gas preheater 12 together and are preheated, after preheating
Gas enter fluidized-bed reactor 4 make positive electrode powder maintain fluidization；The reacted carrier gas preheater 9 of another way carrier gas is pre-
Enter reaction raw materials generator 10 after heat and heat reaction raw materials, reacted raw material nozzles 11 enter stream together with reaction raw materials steam
Fluidized bed reactor 4；Vapor deposition reaction occurs for mixed gas in fluidized-bed reactor 4, and metal oxide deposition is coated on powder
Body surface face, reaction end gas are discharged from the gas outlet of fluidized-bed reactor 4 again, sequentially enter primary cyclone 13, second level rotation
Wind separator 14 and bagroom 15 are discharged, into hydrochloric acid tail gas from the gas outlet of bagroom 15 after separation is gathered dust
Absorber 16 carries out absorption processing, forms byproduct, and exhaust gas is expelled directly out.
Embodiment 3
Using cladding process as described in example 2, by ternary nickel-cobalt lithium manganate material by feed bin 1 through 2 He of screw-feeder
Inlet valve 3 enters in fluidized-bed reactor 4, is 120 DEG C by the nitrogen temperature after reaction carrier gas preheater 9, former into reaction
Expect that generator 10 heats reaction raw materials trimethyl aluminium, it is anti-to enter fluidized bed for reacted raw material nozzles 11 together with trimethyl aluminium steam
Device 4 is answered, meanwhile, after another way nitrogen is preheated by fluidized carrier gas preheater 12, gaseous mixture is formed with vapor and enters fluidized bed
Reactor 4, wherein the mass ratio of vapor and trimethyl aluminium is 1:2, and in fluidized-bed reactor 4 vapor phase hydrolysis occurs for two-way gas
Reaction, in positive electrode powder granule surface depositing metal oxide, reaction temperature is 250 DEG C, and the reaction time is 10 minutes.Instead
Powder is flowed out by fluidized-bed bottom after answering, and is entered cooling in reactor product cooler 6 by outlet valve 5, is collected after cooling into product
Device 7 prepares aluminum oxide cladding ternary nickel cobalt lithium manganate, and wherein metal oxide coats quality percentage
Number be 0.08%, aluminum oxide coat ternary nickel-cobalt lithium manganate material particle electron scanning micrograph as shown in Fig. 2,
Figure it is seen that ternary nickel-cobalt lithium manganate material particle surface has the aluminum oxide of a tunic shape.
Embodiment 4
Using cladding process as described in example 2, by ternary nickel-cobalt lithium manganate material by feed bin 1 through 2 He of screw-feeder
Inlet valve 3 enters in fluidized-bed reactor 4, is 150 DEG C by the temperature of argon gas after reaction carrier gas preheater 9, former into reaction
Expect that generator 10 heats reaction raw materials titanium tetrachloride, it is anti-to enter fluidized bed for reacted raw material nozzles 11 together with titanium tetrachloride vapors
Device 4 is answered, meanwhile, after another way argon gas is preheated by fluidized carrier gas preheater 12, gaseous mixture is formed with vapor and enters fluidized bed
Reactor 4, wherein the mass ratio of vapor and titanium tetrachloride is 1:5, and in fluidized-bed reactor 4 vapor phase hydrolysis occurs for two-way gas
Reaction, in positive electrode powder granule surface depositing metal oxide, reaction temperature is 600 DEG C, and the reaction time is 30 minutes.Instead
Powder is flowed out by fluidized-bed bottom after answering, and is entered cooling in reactor product cooler 6 by outlet valve 5, is collected after cooling into product
Device 7 prepares coated by titanium dioxide ternary nickel cobalt lithium manganate, and wherein metal oxide coats mass percent
Be 3%, the electron microscope of coated by titanium dioxide ternary nickel cobalt lithium manganate as shown in figure 3, from figure 3, it can be seen that
Ternary nickel-cobalt lithium manganate material particle surface has the titanium dioxide of a tunic shape.
Embodiment 5
Using cladding process as described in example 2, by ternary nickel cobalt lithium aluminate material by feed bin 1 through 2 He of screw-feeder
Inlet valve 3 enters in fluidized-bed reactor 4, is 150 DEG C by the neon temperature after reaction carrier gas preheater 9, former into reaction
Expect that generator 10 heats one Chlorodimethyl aluminium of reaction raw materials, reacted raw material nozzles 11 enter together with a Chlorodimethyl aluminum vapor
Fluidized-bed reactor 4, meanwhile, another way neon by fluidized carrier gas preheater 12 preheat after, with vapor formed gaseous mixture into
Fluidized bed reactor 4, wherein the mass ratio of vapor and a Chlorodimethyl aluminium is 1:4, and two-way gas is in fluidized-bed reactor 4
Vapor phase hydrolysis reaction occurs, in positive electrode powder granule surface depositing metal oxide, reaction temperature is 350 DEG C, when reaction
Between be 24 minutes.Powder is flowed out by fluidized-bed bottom after reaction, enters cooling in reactor product cooler 6 by outlet valve 5, after cooling
Into product collector 7, aluminum oxide cladding ternary nickel cobalt lithium aluminate composite positive pole is prepared, wherein metal oxide
Coating mass percent is 2.02%.
Embodiment 6
Using cladding process as described in example 2, by lithium-rich manganese base material by feed bin 1 through screw-feeder 2 and inlet valve 3
It is 180 DEG C by the helium temperature after reaction carrier gas preheater 9, into reaction raw materials generator into fluidized-bed reactor 4
10 heating reaction raw materials alchlors, reacted raw material nozzles 11 enter fluidized-bed reactor 4 together with alchlor steam, together
When, after another way helium is preheated by fluidized carrier gas preheater 12, gaseous mixture is formed with vapor and enters fluidized-bed reactor 4,
Wherein the mass ratio of vapor and alchlor is 1:5, and in fluidized-bed reactor 4 vapor phase hydrolysis reaction occurs for two-way gas,
Positive electrode powder granule surface depositing metal oxide, reaction temperature are 450 DEG C, and the reaction time is 12 minutes.Powder after reaction
Body is flowed out by fluidized-bed bottom, enters cooling in reactor product cooler 6 by outlet valve 5, product collector 7, system are entered after cooling
Standby aluminum oxide out coats lithium-rich manganese-based composite positive pole, and wherein metal oxide cladding mass percent is 1.05%.
Embodiment 7
Using cladding process as described in example 2, by lithium iron silicate material cannot by feed bin 1 through screw-feeder 2 and inlet valve 3
It is 300 DEG C by the nitrogen temperature after reaction carrier gas preheater 9, into reaction raw materials generator into fluidized-bed reactor 4
10 heating reaction raw materials tetraisopropyl titanates, it is anti-to enter fluidized bed for reacted raw material nozzles 11 together with tetraisopropyl titanate steam
Device 4 is answered, meanwhile, after another way nitrogen is preheated by fluidized carrier gas preheater 12, gaseous mixture is formed with vapor and enters fluidized bed
Reactor 4, wherein the mass ratio of vapor and tetraisopropyl titanate is 1:8, and in fluidized-bed reactor 4 gas phase occurs for two-way gas
Hydrolysis, in positive electrode powder granule surface depositing metal oxide, reaction temperature is 450 DEG C, and the reaction time is 14 points
Clock.Powder is flowed out by fluidized-bed bottom after reaction, is entered cooling in reactor product cooler 6 by outlet valve 5, is entered product after cooling
Collector 7 prepares coated by titanium dioxide ferric metasilicate lithium composite positive pole, and wherein metal oxide cladding mass percent is
1.27%.
Embodiment 8
Using cladding process as described in example 2, by LiFePO 4 material by feed bin 1 through screw-feeder 2 and inlet valve 3
It is 220 DEG C by the nitrogen temperature after reaction carrier gas preheater 9, into reaction raw materials generator into fluidized-bed reactor 4
10 heating reaction raw materials four (dimethylamino) zirconiums, reacted raw material nozzles 11 enter together with four (dimethylamino) zirconium steams
Fluidized-bed reactor 4, meanwhile, another way nitrogen by fluidized carrier gas preheater 12 preheat after, with vapor formed gaseous mixture into
Fluidized bed reactor 4, wherein the mass ratio of vapor and four (dimethylamino) zirconiums is 1:7, and two-way gas is anti-in fluidized bed
Answer device 4 that vapor phase hydrolysis reaction occurs, in positive electrode powder granule surface depositing metal oxide, reaction temperature is 550 DEG C, instead
It is 10 minutes between seasonable.Powder is flowed out by fluidized-bed bottom after reaction, enters cooling in reactor product cooler 6 by outlet valve 5, cold
But enter product collector 7 afterwards, prepare zirconia-coated iron phosphate compound anode material of lithium, wherein metal oxide coats
Mass percent is 0.95%.
Embodiment 9
Using cladding process as described in example 2, by LiFePO 4 material by feed bin 1 through screw-feeder 2 and inlet valve 3
It is 280 DEG C by the temperature of argon gas after reaction carrier gas preheater 9, into reaction raw materials generator into fluidized-bed reactor 4
10 heating reaction raw materials n-butoxy zirconiums, reacted raw material nozzles 11 enter fluidized-bed reactor together with n-butoxy zirconium steam
4, meanwhile, after another way argon gas is preheated by fluidized carrier gas preheater 12, gaseous mixture is formed with vapor and enters fluidized-bed reaction
Device 4, wherein the mass ratio of vapor and n-butoxy zirconium is 1:10, and in fluidized-bed reactor 4 vapor phase hydrolysis occurs for two-way gas
Reaction, in positive electrode powder granule surface depositing metal oxide, reaction temperature is 360 DEG C, and the reaction time is 20 minutes.Instead
Powder is flowed out by fluidized-bed bottom after answering, and is entered cooling in reactor product cooler 6 by outlet valve 5, is collected after cooling into product
Device 7 prepares zirconia-coated iron phosphate compound anode material of lithium, and wherein metal oxide cladding mass percent is
1.62%.
Embodiment 10
Using cladding process as described in example 2, by cobalt acid lithium material by feed bin 1 through screw-feeder 2 and inlet valve 3 into
It is 160 DEG C by the nitrogen temperature after reaction carrier gas preheater 9, into reaction raw materials generator 10 in fluidized bed reactor 4
Reaction raw materials zirconium chloride is heated, reacted raw material nozzles 11 enter fluidized-bed reactor 4 together with zirconium chloride steam, together
When, after another way nitrogen is preheated by fluidized carrier gas preheater 12, gaseous mixture is formed with vapor and enters fluidized-bed reactor 4,
Wherein the mass ratio of vapor and zirconium chloride is 1:6, and in fluidized-bed reactor 4 vapor phase hydrolysis reaction occurs for two-way gas,
Positive electrode powder granule surface depositing metal oxide, reaction temperature are 200 DEG C, and the reaction time is 20 minutes.Powder after reaction
Body is flowed out by fluidized-bed bottom, enters cooling in reactor product cooler 6 by outlet valve 5, product collector 7, system are entered after cooling
Standby zirconia-coated cobalt acid lithium composite positive pole out, wherein metal oxide cladding mass percent is 1.45%.
Embodiment 11
Using cladding process as described in example 2, by lithium manganate material by feed bin 1 through screw-feeder 2 and inlet valve 3 into
It is 180 DEG C by the nitrogen temperature after reaction carrier gas preheater 9, into reaction raw materials generator 10 in fluidized bed reactor 4
It heats reaction raw materials three (isopropylcyclopentadiene) and changes cerium, the reacted raw material together with three (isopropylcyclopentadienes) change cerium steam
Nozzle 11 enters fluidized-bed reactor 4, meanwhile, after another way nitrogen is preheated by fluidized carrier gas preheater 12, with vapor shape
Enter fluidized-bed reactor 4 at gaseous mixture, it is 1:13 that wherein vapor and three (isopropylcyclopentadienes), which change the mass ratio of cerium, two
In fluidized-bed reactor 4 vapor phase hydrolysis reaction occurs for road gas, in positive electrode powder granule surface depositing metal oxide, instead
Answering temperature is 450 DEG C, and the reaction time is 4 minutes.Powder is flowed out by fluidized-bed bottom after reaction, enters product by outlet valve 5
It is cooling in cooler 6, enter product collector 7 after cooling, prepares cerium sesquioxide cladding lithium manganate composite anode material,
Middle metal oxide cladding mass percent is 0.05%.
Embodiment 12
Using cladding process as described in example 2, by ternary nickel-cobalt lithium manganate material by feed bin 1 through 2 He of screw-feeder
Inlet valve 3 enters in fluidized-bed reactor 4, is 180 DEG C by the nitrogen temperature after reaction carrier gas preheater 9, former into reaction
Expect that generator 10 heats reaction raw materials three (isopropylcyclopentadienyl) lanthanum, together with three (isopropylcyclopentadienyl) lanthanum steams
Reacted raw material nozzles 11 enter fluidized-bed reactor 4, meanwhile, after another way nitrogen is preheated by fluidized carrier gas preheater 12,
Gaseous mixture is formed with vapor and enters fluidized-bed reactor 4, wherein the quality of vapor and three (isopropylcyclopentadienyl) lanthanums
Than for 1:17, in fluidized-bed reactor 4 vapor phase hydrolysis reaction occurs for two-way gas, gold is deposited on positive electrode powder granule surface
Belong to oxide, reaction temperature is 380 DEG C, and the reaction time is 20 minutes.Powder is flowed out by fluidized-bed bottom after reaction, passes through discharging
Valve 5 enters cooling in reactor product cooler 6, enters product collector 7 after cooling, prepares lanthanum sesquioxide cladding ternary nickel cobalt manganese
Sour lithium composite positive pole, wherein metal oxide cladding mass percent is 1.03%.
Embodiment 13
Using cladding process as described in example 2, by ternary nickel-cobalt lithium manganate material by feed bin 1 through 2 He of screw-feeder
Inlet valve 3 enters in fluidized-bed reactor 4, is 160 DEG C by the nitrogen temperature after reaction carrier gas preheater 9, former into reaction
Expect that generator 10 heats reaction raw materials Triisopropoxyvanadium(V) oxide, reacted raw material nozzles 11 enter together with Triisopropoxyvanadium(V) oxide steam
Fluidized-bed reactor 4, meanwhile, another way nitrogen by fluidized carrier gas preheater 12 preheat after, with vapor formed gaseous mixture into
Fluidized bed reactor 4, wherein the mass ratio of vapor and Triisopropoxyvanadium(V) oxide is 1:5, and two-way gas is in fluidized-bed reactor 4
Vapor phase hydrolysis reaction occurs, in positive electrode powder granule surface depositing metal oxide, reaction temperature is 450 DEG C, when reaction
Between be 18 minutes.Powder is flowed out by fluidized-bed bottom after reaction, enters cooling in reactor product cooler 6 by outlet valve 5, after cooling
Into product collector 7, vanadic anhydride cladding ternary nickel cobalt lithium manganate is prepared, wherein metal oxide
Coating mass percent is 0.09%.
Technological parameter (such as temperature, time) section bound value of the invention and interval value can realize this law,
Embodiment numerous to list herein.
Ordinary skill in the art knowledge can be used in the unspecified content of the present invention.
It should be noted last that the above examples are only used to illustrate the technical scheme of the present invention and are not limiting.Although ginseng
It is described the invention in detail according to embodiment, it will be apparent to an ordinarily skilled person in the art that technical side of the invention
Case is modified or replaced equivalently, and without departure from the spirit and scope of technical solution of the present invention, should all be covered in the present invention
Scope of the claims in.
Claims (7)
1. a kind of system of anode material for lithium-ion batteries metal oxide coating modification, which is characterized in that the system comprises
Feed bin (1), screw-feeder (2), inlet valve (3), fluidized-bed reactor (4), outlet valve (5), reactor product cooler (6), product
Collector (7), burner (8), reaction carrier gas preheater (9), reaction raw materials generator (10), reaction raw materials nozzle (11), stream
Change carrier gas preheater (12), primary cyclone (13), secondary cyclone (14), bagroom (15) and hydrochloric acid tail
Aspiration device (16)；
The discharge port of the feed bin (1) is connected with the feed inlet of screw-feeder (2), the discharging of the screw-feeder (2)
Mouth is connected with the feed inlet of inlet valve (3), the feed inlet phase of the discharge port and fluidized-bed reactor (4) of the inlet valve (3)
Connection, the air inlet of the fluidized-bed reactor (4) are connected with the gas outlet of fluidized carrier gas preheater (12)；The fluidized bed
The air inlet of reactor (4) is connected with the gas outlet of reaction raw materials nozzle (11), the air inlet of reaction raw materials nozzle (11) with
The gas outlet of reaction raw materials generator (10) is connected, the air inlet of reaction raw materials generator (10) with react carrier gas preheater
(9) gas outlet is connected, and the discharge port of the fluidized-bed reactor (4) is connected with the feed inlet of inlet valve (5), inlet valve
(5) discharge port is connected with the feed inlet of reactor product cooler (6), the discharge port of reactor product cooler (6) and product collector (7)
Feed inlet be connected；The gas outlet of fluidized-bed reactor (4) is connected with the air inlet of primary cyclone (13), level-one
The gas outlet of cyclone separator (13) is connected with the air inlet of secondary cyclone (14), primary cyclone (13) and
The discharge port of secondary cyclone (14) is connected with the feed inlet of fluidized-bed reactor (4), secondary cyclone (14)
Gas outlet be connected with the air inlet of bagroom (15), the discharge port and fluidized-bed reactor of bagroom (15)
(4) feed inlet is connected, and the gas outlet of bagroom (15) is connected with the air inlet of hydrochloric acid tail gas absorption device (16)；Combustion
The gas outlet of burner (8) is connected with the air inlet for reacting carrier gas preheater (9) and fluidized carrier gas preheater (12).
2. a kind of method of anode material for lithium-ion batteries metal oxide coating modification, comprising the following steps:
1) positive electrode powder is stopped through screw-feeder (2) and inlet valve (3) into fluidized-bed reactor (4) by feed bin (1)
Certain time returns to stream after the collection of primary cyclone (13), secondary cyclone (14) and bagroom (15)
Fluidized bed reactor (4)；
2) coal gas is exchanged heat after burner (8) heating by reaction carrier gas preheater (9) and fluidized carrier gas preheater (12),
The gas of preheating gas, the discharge that exchanges heat directly is discharged with exhaust gas；Carrier gas and water are sent into fluidized carrier gas preheater (12) progress together
Preheating, the mixed gas after preheating, which enters fluidized-bed reactor (4), makes positive electrode powder maintain fluidization；Another way carrier gas warp
Enter reaction raw materials generator (10) heating reaction raw materials after reacting carrier gas preheater (9) preheating, together with reaction raw materials steam
Reacted raw material nozzles (11) enter fluidized-bed reactor (4)；Mixed gas is vapor-deposited in fluidized-bed reactor (4)
Reaction, metal oxide deposition are coated on positive electrode powder surface, form clad, the discharging from fluidized-bed reactor (4)
After mouth discharge, enter reactor product cooler (6) through outlet valve (5) and cooled down, enters product collector (7) after cooling, reaction tail
Gas is discharged from the gas outlet of fluidized-bed reactor (4) again, sequentially enters primary cyclone (13), secondary cyclone
(14) it is inhaled from the discharge of the gas outlet of bagroom (15) after separation is gathered dust into hydrochloric acid tail gas with bagroom (15)
It receives device (16) and carries out absorption processing, form byproduct, exhaust gas is expelled directly out.
3. the method for anode material for lithium-ion batteries metal oxide coating modification according to claim 2, feature exist
In the positive electrode powder is ternary nickle cobalt lithium manganate, ternary nickel cobalt lithium aluminate, lithium-rich manganese-based, ferric metasilicate lithium, ferric phosphate
One of lithium, cobalt acid lithium and LiMn2O4.
4. the method for anode material for lithium-ion batteries metal oxide coating modification according to claim 2, feature exist
In the metal oxide is aluminum oxide, titanium dioxide, zirconium dioxide, cerium sesquioxide, lanthanum sesquioxide and five oxidations
One of two vanadium, the mass percent of the metal oxide of cladding are 0.05~3%.
5. the method for anode material for lithium-ion batteries metal oxide coating modification according to claim 4, feature exist
In the metal oxide of the reaction raw materials and cladding has corresponding relationship, and corresponding aluminum oxide, reaction raw materials are trimethyls
One of aluminium, a Chlorodimethyl aluminium and alchlor；Corresponding titanium dioxide, reaction raw materials are four isopropyls of titanium tetrachloride and metatitanic acid
One of ester；Corresponding zirconium dioxide, reaction raw materials are one in four (dimethylamino) zirconiums, n-butoxy zirconium and zirconium chloride
Kind；Corresponding cerium sesquioxide, reaction raw materials are that three (isopropylcyclopentadienes) change cerium；Corresponding lanthanum sesquioxide, reaction raw materials are
Three (isopropylcyclopentadienyl) lanthanums；Corresponding vanadic anhydride, reaction raw materials are Triisopropoxyvanadium(V) oxides.
6. the method for anode material for lithium-ion batteries metal oxide coating modification according to claim 2, feature exist
In the carrier gas is the combination of one of nitrogen, helium, argon gas, neon or at least two, by reacting carrier gas preheater
(9) carrier gas temperature after is 120~300 DEG C.
7. the method for anode material for lithium-ion batteries metal oxide coating modification according to claim 2, feature exist
In, the carrier gas forms gaseous mixture with vapor and enters fluidized-bed reactor (4) after fluidized carrier gas preheater (12) preheat,
It is hydrolyzed by reaction raw materials gas phase, in positive electrode powder granule surface depositing metal oxide, the vapor phase hydrolysis process is logical
The mass ratio for entering vapor and reaction raw materials is 1:2~1:17, and reaction temperature is 200~600 DEG C, and positive electrode powder is fluidizing
Residence time in bed reactor (4) is 4~30 minutes.
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