CN109786689A - Anode material of lithium battery presoma, preparation, processing and doping type anode material of lithium battery with film nuclear structure - Google Patents
Anode material of lithium battery presoma, preparation, processing and doping type anode material of lithium battery with film nuclear structure Download PDFInfo
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- CN109786689A CN109786689A CN201811570984.1A CN201811570984A CN109786689A CN 109786689 A CN109786689 A CN 109786689A CN 201811570984 A CN201811570984 A CN 201811570984A CN 109786689 A CN109786689 A CN 109786689A
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The present invention relates to a kind of anode material of lithium battery presoma with film nuclear structure, preparation, processing and doping type anode material of lithium battery, by atomic layer deposition method in anode material of lithium battery presoma body surface, the metal or metal compound film of one layer of cladding or multilayer for doping, form the anode material of lithium battery presoma with film nuclear structure.Anode material of lithium battery presoma with film nuclear structure can form doping type presoma by calcining, then mix lithium and re-sinter to form doping type positive electrode.Alternatively, the anode material of lithium battery presoma with film nuclear structure is directly mixed with lithium source, then sintering forms doping type positive electrode.The present invention compares existing anode material doped method, and component and the content control for the doping that the present invention is formed are more accurate, and doping more evenly, and does not influence the pattern and structure of presoma and positive electrode.
Description
Technical field
The present invention relates to the positive electrode technical field of lithium battery more particularly to a kind of anode material of lithium battery presomas
And preparation, doping type anode material of lithium battery.
Background technique
Lithium ion battery is the Battery Market of a rapid growth.They have important application, including hand in numerous areas
Machine, hybrid vehicle and plug-in power vehicle.Oxide that these batteries are usually made of the transition metal containing lithium or
Transition metal phosphate anode and graphite cathode containing lithium.The energy density of lithium ion battery dramatically depends on positive material
Expect the selection of type, current high-energy-density, low cost, long-life and safety positive electrode be prior development direction.High voltage
Cobalt acid lithium, high pressure LiMn2O4, high capacity LiFePO4, nickelic ternary material, NCA, the positive electrodes such as rich lithium are all great development
The material of prospect, however this kind of material can show quick inducing capacity fading and impedance rise in cyclic process, and heat is surely
The problems such as qualitative difference.Such as the poor reason of cycle performance and thermal stability of nickelic tertiary cathode essentially consists in:
1) Li/Ni is easy to happen mixing, and nickelic anode is even more serious.Due to Ni2+With Li+Radius is close, in de- lithium mistake
Cheng Zhong, Li+Deintercalation forms vacancy, Ni2+It is readily migrate into lithium position, to cause the precipitation of lithium, is constantly repeating reaction process
In, mixing ratio increases, and material hierarchical structure collapses, and causes performance substantially to weaken, therefore cycle performance is poor；
2) in ternary material Ni content increase, thermal decomposition temperature reduce, thermal discharge increase, material thermal stability be deteriorated.
In addition, nickelic anode Ni4+Content is high, Ni4+Have strong oxidizing property, electrolyte can be decomposed, in order to keep charge balance, in material
Oxygen can be released, crystal structure is destroyed, to make the bad stability of material.
General nickelic anode is needed using bulk phase-doped modified promotion material property, by change material lattice constant or
The valence state of Partial Elements improves the stability of material structure in material, improves the electronic conductivity and ionic conductivity of material,
Reduce cationic mixing.Doping is broadly divided into cation doping (Al, Mg, Ti, Zr, Mo, Cr), anion doped (F) and yin-yang
Ion co-doped (AlF3, MgF2) etc..In addition the distributed controll of doped chemical, such as gradient type distribution (such as nickelic ternary material
Ni concentration gradually decreases from internal to external, and doped chemical concentration distribution gradually rises from internal to external) it is also to promote height
A kind of important method of nickel ternary material electrochemical stability.
The core technology of nickelic positive electrode is doping process, industrializes the master that tertiary cathode material production uses at present
Stream production technology is that coprecipitation prepares presoma, it is then mixed solid-phase sintering with lithium source, ternary material is made, be entrained in
Presoma and sintering link.Doping process can be characterized as being entrained in the uniformity of positive electrode body Xiangli, and doping is more
Few control, the distribution situation etc. of doped chemical.The quality of doping process, can directly determine positive electrode crystal structure,
Performance in terms of microscopic appearance and chemical property.
Current doping process process, which can be divided mainly into 1) precursor doped and 2) mix in lithium sintering, adulterates two kinds of forms:
1) be by undoped anode material of lithium battery presoma and lithium source (usually lithium carbonate or lithium hydroxide), with
And metallic element (such as nano aluminium oxide, the nano-titanium oxide or basic magnesium carbonate etc.) mixing for needing to adulterate, then it is sintered,
Form doping type anode material of lithium battery；
2) be first to the presoma of anode material of lithium battery (such as ternary precursor nickel cobalt manganese hydroxide or cobalt acid
Lithium presoma cobaltosic oxide etc.) realize doping, then by the positive electrode material precursor and lithium source (usually lithium carbonate after doping
Or lithium hydroxide) mixing sintering, form doping type anode material of lithium battery.
The mixing (mixing and doping object and positive electrode material precursor) of both doping way mainly passes through mechanical stirring at present
Method comes mixing and doping substance and lithium battery anode persursor material, or passes through liquid phase coprecipitation, hydro-thermal method or collosol and gel
Method etc. realizes the mixing of positive presoma and dopant material.Above mixing (the mixing and doping object and positive electrode material precursor) method
The shortcomings that it is mainly uneven, it is difficult to control, cause doping in sintered positive electrode material precursor or positive electrode body phase
Unevenly, concentration distribution is difficult to control.And liquid phase method industrial production complex process, difficulty are high.Such as chemical coprecipitation technique relies on
The long great achievement offspring of nanoscale primary particle reunion, in coprecipitation process, it is unordered that violent stirring will affect primary particle
Distribution is reunited, and causes second particle growth out of control.In addition, the element that doping is added in coprecipitation process also will affect positive material
Expect that the nucleating growth of second particle, pattern change, stress variation etc., so that positive electrode degradation or not proposing after doping
Height, and be co-precipitated in multi-element doping, gradient type distribution doping aspect also faces many technical challenges.
Summary of the invention
Technical problem to be solved by the invention is to provide a kind of anode material of lithium battery presomas with film nuclear structure
And preparation, processing, doping type anode material of lithium battery, the comprehensive performance of anode material of lithium battery is improved, and then improve battery
Stability.
In order to solve the above technical problems, the present invention proposes a kind of anode material of lithium battery presoma with film nuclear structure,
Including presoma ontology and the film for being evenly coated at presoma body surface, the film is the doping of anode material of lithium battery
Metal or metal oxide or metal nitride or metal chloride or metal halide or metal fluoride or metal
Sulfide or one or more of III-V element compound or two or six group element compounds material, pass through atomic layer deposition
Method is grown；The film thickness is 0.2 sodium rice to 1000 nanometers.
The presoma ontology is nickel cobalt manganese hydroxide (NixCoyMnz)OH2, cobaltosic oxide Co3O4, manganese dioxide
MnO2, mangano-manganic oxide Mn3O4Or FePO4。
The preparation method of anode material of lithium battery presoma with film nuclear structure, comprising the following steps:
A. lithium battery anode presoma bulk powder material is placed in atomic layer deposition reaction chamber, heats reaction chamber temperature
To 250~1000 Kelvins, lithium battery anode presoma bulk powder material powder is made to keep 1~1000 point at such a temperature
Clock；
B. it is passed through cleaning gas, is cleaned 0~6000 minute；
C. gaseous precursor A or precursor A containing doped chemical are passed through and takes sparkling mixture, time 0.01
~10000 seconds, then keep 1 second~500 minutes a period of time；
D. it is passed through cleaning gas, cleans 0.1~1000 minute, removes extra byproduct of reaction；
E. precursor B or precursor B are passed through and takes sparkling mixture, the time is 0.01~10000 second, is then kept
1 second for a period of time~500 minutes；
F. it is passed through cleaning gas, cleans 0.1~1000 minute, removes extra byproduct of reaction；
G. circulation executes step c-f, until obtaining required 0.2 sodium rice of cladding thickness to 1000 nanometers.
Preferably, the clad speed of growth is the every circulation of 1 to 100 Ethylmercurichlorendimides, a circular in definition be the step c extremely
Step f.
It advanced optimizes, before step a, the lithium battery anode presoma bulk powder material passes through O2, N2O,
NO2, NH3, H2S, F2, HF, N2, H2, the corona treatment of inert gas or above-mentioned gas, treatment temperature is 250~1200
Kelvin, time are 0~300 minute.
Gas fluidized using mechanical oscillation or rotation during the step a-f, ultrasonic wave mode is to atomic layer deposition
Lithium battery anode presoma bulk powder material implementation in product reaction chamber is grain fluidized, to realize uniform coated.
Preferably, it is trimethyl aluminium, alchlor, tetraisopropyl titanate, titanium tetrachloride, hafnium acid that the precursor A, which is selected,
Tetra-isopropyl, two luxuriant magnesium and sodium, calcium, zinc, magnesium, aluminium, iron, copper, yttrium, chromium, manganese, tungsten, silicon, titanium, zirconium, hafnium, lanthanum, tantalum, molybdenum, lithium,
One or more of boron, phosphorus, the metallo-organic compound of fluorine, halide, alkoxide, metal p-diketonates complex compound, fluoride
Mixture.
Preferably, the precursor B is water, oxygen, ozone, hydrogen peroxide, plasma oxygen atom, ammonia, plasma nitrogen
Atom, plasma hydrogen atom, hydrogen sulfide, fluorine gas, the mixture of one or several substances of hydrofluoric acid.
The cleaning gas is nitrogen or argon gas；Carrying gas is nitrogen or argon gas.
The present invention provides the processing method of the anode material of lithium battery presoma with film nuclear structure, by it is described just
The sintering of pole material precursor, sintering temperature are 250-1500 Kelvin, and sintering atmosphere is vacuum, air, oxygen or argon gas, sintering
Time is 1-24 hours, so that the thermal expansion in calcination process of the element of cladding is scattered to inside presoma, forms doping type presoma.
Invention also provides a kind of doping type anode material of lithium battery using the doping type precursor preparation.It will
The doping type presoma is sintered after mixing with lithium source, sintering temperature 250-1500 Kelvin, and sintering time 1-24 hours, sintering
Atmosphere is vacuum, air, oxygen or argon gas, and making the element coated, thermal expansion is scattered to inside positive electrode during the sintering process, is obtained
The doping type anode material of lithium battery.
The present invention goes back while providing another doping type lithium battery anode material using the doping type precursor preparation
Material.It is sintered after the anode material of lithium battery presoma with film nuclear structure is directly mixed with lithium source, sintering temperature 250-
1500 Kelvins, time 1-24 hour, sintering atmosphere are vacuum, air, oxygen or argon gas, realize the element of cladding sintered
Thermal expansion is scattered to inside positive electrode in journey, forms doping type anode material of lithium battery.
The doped chemical of the doping type anode material of lithium battery include sodium, calcium, zinc, magnesium, aluminium, yttrium, iron, copper, chromium,
Tungsten, manganese, silicon, titanium, zirconium, hafnium, lanthanum, tantalum, molybdenum, lithium, boron, phosphorus, fluorine one or more of mixture.
Than existing anode material doped method, the control precision of atomic layer deposition method cladding thickness can achieve 0.1nm,
Cladding accuracy of measurement can achieve 10-50ppm rank, therefore the component of doping that is formed of the present invention and content control are more accurate.
And since atomic layer deposition coats very complete, also more evenly, final uniform doping, distributivity is also more for presoma cladding
It is good, and then improve the chemical property of lithium battery.In addition, atomic layer deposition method coats presoma ontology, do not change forerunner substantially
The internal structure and pattern of body bulk material, such as liquid-phase coprecipitation prepare ternary material precursor, and dopant material can be to preceding
Drive body bulk material ultimately generate pattern and structure has a significant impact, therefore this method coat presoma, or doping forerunner
Body technology is opposite to be easier to realize and operate.
Detailed description of the invention
Technical solution of the present invention is further described in detail with reference to the accompanying drawings and detailed description.
Fig. 1 is the preparation of the anode material of lithium battery presoma with film nuclear structure, is processed into showing for doping type presoma
It is intended to.
Fig. 2 is one kind that the present invention prepares doping type anode material of lithium battery using anode material of lithium battery presoma ontology
Embodiment schematic diagram.
Fig. 3 is that the present invention utilizes anode material of lithium battery presoma ontology to prepare the another of doping type anode material of lithium battery
Kind embodiment schematic diagram.
Fig. 4 is nickelic ternary battery capacity variation produced by the present invention relative to battery charging and discharging cycle-index curve graph.
Specific embodiment
As shown in Figure 1,1 surface of presoma ontology is by atomic layer deposition method growing film 2, being formed has film nuclear structure
Anode material of lithium battery presoma 3.2 material of film is the doping metals or metal oxide or metal of anode material of lithium battery
Nitride or metal chloride or metal halide or metal fluoride or metal sulfide or III-V element chemical combination
One or more of object or two or six group element compounds material；Film thickness is 0.2 sodium rice to 1000 nanometers.Presoma sheet
Body 1 is nickel cobalt manganese hydroxide (NixCoyMnz)OH2, cobaltosic oxide Co3O4, manganese dioxide MnO2, mangano-manganic oxide Mn3O4,
Or FePO4.Anode material of lithium battery presoma 3 with film nuclear structure is sintered, sintering temperature is 250-1500 Kelvin, is burnt
Knot atmosphere is vacuum, air, oxygen or argon gas, and sintering time is 1-24 hours, so that the element of cladding is warm in calcination process
It is diffused into inside presoma, forms doping type presoma 4.
As shown in Fig. 2, being sintered after doping type presoma 4 is mixed with lithium source 5, sintering temperature 250-1500 Kelvin, burn
Knot time 1-24 hours, sintering atmosphere are vacuum, air, oxygen or argon gas, make the element thermal diffusion during the sintering process of cladding
To inside positive electrode, the doping type anode material of lithium battery 6 is obtained.
As shown in figure 3, be sintered after the anode material of lithium battery presoma 3 with film nuclear structure is directly mixed with lithium source 5,
Sintering temperature 250-1500 Kelvin, time 1-24 hour, sintering atmosphere are vacuum, air, oxygen or argon gas, realize cladding
Thermal expansion is scattered to inside positive electrode element during the sintering process, forms doping type anode material of lithium battery 6.
The doped chemical of doping type anode material of lithium battery include sodium, calcium, zinc, magnesium, aluminium, yttrium, iron, copper, chromium, tungsten, manganese,
Silicon, titanium, zirconium, hafnium, lanthanum, tantalum, molybdenum, lithium, boron, phosphorus, fluorine one or more of mixture.
As shown in figure 4, the curve of almost horizontal is to adulterate using made from doping type anode material of lithium battery of the present invention
Nickelic ternary battery capacity, curve obliquely is undoped nickelic ternary battery, voltage > 4.35V 0.5C.Obviously, it mixes
The battery capacity variation of the nickelic ternary battery of miscellaneous mistake increases no significant change relative to battery charging and discharging cycle-index.And not
The battery capacity variation of the nickelic ternary battery of doping increases relative to battery charging and discharging cycle-index is presented rapid decrease trend.
This difference becomes apparent under high power charging-discharging.
Prepare the anode material of lithium battery presoma with film nuclear structure, comprising the following steps:
Lithium battery anode presoma bulk powder material passes through O2, N2O,NO2, NH3, H2S, F2, HF, N2, H2, inert gas
Or the corona treatment of above-mentioned gas, treatment temperature are 250~1200 Kelvins, the time is 0~300 minute；
A. lithium battery anode presoma bulk powder material is placed in atomic layer deposition reaction chamber, heats reaction chamber temperature
To 250~1000 Kelvins, lithium battery anode presoma bulk powder material powder is made to keep 1~1000 point at such a temperature
Clock；
B. it is passed through cleaning gas, is cleaned 0~6000 minute；
C. gaseous precursor A or precursor A containing doped chemical are passed through and takes sparkling mixture, time 0.01
~10000 seconds, then keep 1 second~500 minutes a period of time；It is trimethyl aluminium, alchlor, metatitanic acid four that precursor A, which is selected,
Isopropyl ester, titanium tetrachloride, hafnium acid tetra-isopropyl, two luxuriant magnesium and sodium, calcium, zinc, magnesium, aluminium, iron, copper, yttrium, chromium, manganese, tungsten, silicon,
Titanium, zirconium, hafnium, lanthanum, tantalum, molybdenum, lithium, boron, phosphorus, the metallo-organic compound of fluorine, halide, alkoxide, metal p-diketonates complex compound, fluorine
The mixture of one or more of compound.
D. it is passed through cleaning gas, cleans 0.1~1000 minute, removes extra byproduct of reaction；
E. precursor B or precursor B are passed through and takes sparkling mixture, the time is 0.01~10000 second, is then kept
1 second for a period of time~500 minutes；Precursor B is water, oxygen, ozone, hydrogen peroxide, plasma oxygen atom, ammonia, plasma
Nitrogen-atoms, plasma hydrogen atom, hydrogen sulfide, fluorine gas, the mixture of one or several substances of hydrofluoric acid.Carry gas be nitrogen or
Argon gas.
F. it is passed through cleaning gas, cleans 0.1~1000 minute, removes extra byproduct of reaction；Cleaning gas is nitrogen or argon
Gas；
G. circulation executes step c-f, until obtaining required 0.2 sodium rice of cladding thickness to 1000 nanometers.
The clad speed of growth is the every circulation of 1 to 100 Ethylmercurichlorendimides, and a circular in definition is the step c to step f.
Gas fluidized using mechanical oscillation or rotation during step a-f, ultrasonic wave mode is anti-to atomic layer deposition
The lithium battery anode presoma bulk powder material in chamber is answered to implement grain fluidized, to realize uniform coated.
Embodiment 1
A. by NCA presoma ontology Ni0.84Co0.16(OH)2Dusty material is placed in atomic layer deposition instrument reaction chamber, is taken out
Vacuum simultaneously heats reaction chamber temperature to 400 Kelvins, and electrode sample is made to keep 25min, the gas in reaction chamber at a set temperature
Pressure is 10 millitorrs；
B. air outlet valve is opened, pulse cleans gas, cleans 15 seconds；
C. air outlet valve, pulsed gaseous trimethyl aluminium are closed, the time is 0.01 second, then keeps 60 seconds a period of times；
D. air outlet valve is then opened, pulse cleans gas argon gas, cleans 1 minute；Air outlet valve is closed, is vacuumized, it is extra to remove
Byproduct of reaction；
E. it is then shut off air outlet valve, pulsed gaseous water, the time is 10 seconds, then keeps a period of time 5s；
F. air outlet valve is then opened, pulse cleans gas argon gas, cleans 1 minute；It is again switched off air outlet valve, is vacuumized, is removed
Extra byproduct of reaction；
G. return step c, circulation execute c-f step.
The clad speed of growth is the every circulation of 1.1 Ethylmercurichlorendimides, coated metal oxide thickness be about 100 Ethylmercurichlorendimides just
Pole material precursor.
Presoma after cladding is directly mixed with lithium source (lithium source may be, but is not limited to lithium hydroxide and lithium carbonate), so
Afterwards by sintering reaction, sintering temperature 250-1500 Kelvin, sintering time 12 hours, sintering atmosphere was including but not limited to true
Sky, air, oxygen or argon gas realize that thermal expansion is scattered to inside positive electrode during the sintering process for the element of cladding, form doping type
NCA-- nickel cobalt aluminium (Li (NixCoyAlz) O2)。
Embodiment 2
A. by presoma ontology mangano-manganic oxide Mn3O4Dusty material is placed in atomic layer deposition instrument reaction chamber, is vacuumized
And reaction chamber temperature is heated to 450 Kelvins, so that electrode sample is kept 5min at a set temperature, the air pressure in reaction chamber is 10
Millitorr；
B. air outlet valve is opened, pulse cleans gas nitrogen, cleans 3s；
C. air outlet valve is closed, the luxuriant magnesium of pulsed gaseous two, the time is 10 seconds, then keeps 1 second a period of time；
D. air outlet valve is then opened, pulse cleans gas nitrogen, cleans 0.1 minute；Air outlet valve is closed, vacuumizes, removes more
Remaining byproduct of reaction；
G. return step c, circulation execute c-f step.
The clad speed of growth is the every circulation of 1.2 Ethylmercurichlorendimides, coated metal oxide thickness be about 50 Ethylmercurichlorendimides just
Pole material precursor.
Presoma after cladding is directly mixed with lithium source (lithium source may be, but is not limited to lithium hydroxide and lithium carbonate), so
Afterwards by sintering reaction, sintering temperature 250-1500 Kelvin, sintering time 16 hours, sintering atmosphere be can include but is not limited to
Vacuum, air, oxygen or argon gas realize that thermal expansion is scattered to inside positive electrode during the sintering process for the element of cladding, form doping
Type LiMn2O4.
Embodiment 3
It a. will be by NCA presoma ontology Ni0.84Co0.16(OH)2It is placed in atomic layer deposition instrument reaction chamber, vacuumizes simultaneously
Reaction chamber temperature is heated to 500 Kelvins, electrode sample is made to keep 5min at a set temperature, the air pressure in reaction chamber is 10 millis
Support；
B. air outlet valve is opened, pulse cleans gas argon gas, cleans 10s；
C. air outlet valve, pulsed gaseous tetraisopropyl titanate are closed, the time is 1 second, then keeps 20 seconds a period of times；
D. air outlet valve is then opened, pulse cleans gas argon gas, cleans 0.5 minute；Air outlet valve is closed, vacuumizes, removes more
Remaining byproduct of reaction；
E. it is then shut off air outlet valve, pulse of ozone, the time is 1 second, then keeps a period of time 30s；
F. air outlet valve is then opened, pulse cleans gas argon gas, cleans 0.1~1 minute；It is again switched off air outlet valve, is vacuumized,
Remove extra byproduct of reaction；
G. return step c, circulation execute c-f step.
The clad speed of growth is the every circulation of 1.2 Ethylmercurichlorendimides, and having been coated metal oxide thickness is about 1000 Ethylmercurichlorendimides
Positive electrode material precursor.
Presoma after cladding is directly mixed with lithium source (lithium source may be, but is not limited to lithium hydroxide and lithium carbonate), so
Afterwards by sintering reaction, sintering temperature 250-1500 Kelvin, sintering time 24 hours, sintering atmosphere be can include but is not limited to
Vacuum, air, oxygen or argon gas realize that thermal expansion is scattered to inside positive electrode during the sintering process for the element of cladding, form doping
Type NCA.
Embodiment 4
A. by presoma ontology FePO4Dusty material is placed in atomic layer deposition instrument reaction chamber, is vacuumized and is heated anti-
It answers room temperature to 550 Kelvins, electrode sample is made to keep 10min at a set temperature, the air pressure in reaction chamber is 5 millitorrs；
B. air outlet valve is opened, pulse cleans the mixture of gas nitrogen and argon gas, cleans 12s；
C. air outlet valve, pulsed gaseous hafnium acid tetra-isopropyl are closed, the time is 0.5 second, then keeps 30 seconds a period of times；
D. air outlet valve is then opened, pulse cleans the mixture of gas nitrogen and argon gas, cleans 0.6 minute；Air outlet valve is closed,
It vacuumizes, removes extra byproduct of reaction；
E. it is then shut off air outlet valve, pulse plasma oxygen atom, the time is 5 seconds, then keeps a period of time 1s；
F. air outlet valve is then opened, pulse cleans the mixture of gas nitrogen and argon gas, cleans 0.2 minute；It is again switched off out
Air valve vacuumizes, and removes extra byproduct of reaction；
G. return step c, circulation execute c-f step.
The clad speed of growth is the every circulation of 1.05 Ethylmercurichlorendimides, and having been coated metal oxide thickness is about 500 Ethylmercurichlorendimides
Positive electrode material precursor.
Presoma after cladding is directly mixed with lithium source (lithium source may be, but is not limited to lithium hydroxide and lithium carbonate), so
Afterwards by sintering reaction, sintering temperature 250-1500 Kelvin, sintering time 4 hours, sintering atmosphere include but is not limited to vacuum,
Air, oxygen or argon gas realize that thermal expansion is scattered to inside positive electrode during the sintering process for the element of cladding, form doping type phosphoric acid
Iron lithium.
Embodiment 5
A. by cobalt acid lithium presoma ontology Co3O4Dusty material body is placed in atomic layer deposition instrument reaction chamber, is vacuumized simultaneously
Reaction chamber temperature is heated to 700 Kelvins, electrode sample is made to keep 30min at a set temperature, the air pressure in reaction chamber is 100
Millitorr；
B. air outlet valve is opened, pulse cleans the mixture of gas nitrogen and argon gas, cleans 8s；
C. air outlet valve, the mixture of pulsed gaseous titanium tetrachloride and hafnium acid tetra-isopropyl are closed, the time is 7 seconds, is then protected
Hold 20 seconds a period of times；
D. air outlet valve is then opened, the mixture of pulsed nitrogen and argon gas cleans 0.3 minute as gas is cleaned；It closes out
Air valve vacuumizes, and removes extra byproduct of reaction；
E. it is then shut off air outlet valve, pulse hydrogen peroxide, the time is 0.02 second, then keeps a period of time 10s；
F. air outlet valve is then opened, pulse cleans the mixture of gas nitrogen and argon gas, cleans 0.8 minute；It is again switched off out
Air valve vacuumizes, and removes extra byproduct of reaction；
G. return step c, circulation execute c-f step.
The clad speed of growth is the every circulation of 1 Ethylmercurichlorendimide, has been coated the anode that metal oxide thickness is about 300 Ethylmercurichlorendimides
Material precursor
Presoma can be 250-1500 Kelvin through oversintering, sintering temperature after cladding, sintering time 18 hours, be sintered
Atmosphere includes but is not limited to vacuum, air, oxygen or argon gas, so that the thermal expansion in calcination process of the element of cladding is scattered to presoma
Inside forms doping type Co3O4Presoma, later by doping type Co3O4(lithium source is not limited to lithium hydroxide to presoma with lithium source
And lithium carbonate) mixing after be sintered, formed doping type cobalt acid lithium.
Embodiment 6
A. by cobalt acid lithium presoma ontology Co3O4Dusty material is placed in atomic layer deposition instrument reaction chamber, is vacuumized and is added
Thermal reaction chamber temperature makes electrode sample keep 5min at a set temperature to 300 Kelvins, and the air pressure in reaction chamber is 50 millis
Support；
B. air outlet valve is opened, pulse cleans gas argon gas, cleans 5s；
C. air outlet valve, pulsed gaseous alchlor and tetraisopropyl titanate mixture are closed, the time is 0.05 second, is then protected
Hold 50 seconds a period of times；
D. air outlet valve is then opened, pulse cleans the mixture of gas gaseous state hydrogen peroxide and oxygen, cleans 1 minute；It closes out
Air valve vacuumizes, and removes extra byproduct of reaction；
E. it is then shut off air outlet valve, pulse fluorine gas, the time is 3 seconds, then keeps a period of time 15s；
F. air outlet valve is then opened, pulse cleans gas argon gas, cleans 0.4 minute；It is again switched off air outlet valve, is vacuumized, is moved
Remove extra byproduct of reaction；
G. return step c, circulation execute c-f step.
The clad speed of growth is the every circulation of 1.15 Ethylmercurichlorendimides, and having been coated metal oxide thickness is about 800 Ethylmercurichlorendimides
Positive electrode material precursor.
Presoma can be 250-1500 Kelvin through oversintering, sintering temperature after cladding, sintering time 1 hour, be sintered
Atmosphere includes but is not limited to vacuum, air, oxygen or argon gas, so that the thermal expansion in calcination process of the element of cladding is scattered to presoma
Inside forms doping type Co3O4Presoma, later by doping type Co3O4Presoma and lithium source (lithium source but are not limited to hydroxide
Lithium and lithium carbonate) mixing after be sintered, formed doping type cobalt acid lithium.
Embodiment 7
A. by presoma ontology mangano-manganic oxide Mn3O4Dusty material is placed in atomic layer deposition instrument reaction chamber, is vacuumized
And reaction chamber temperature is heated to 250 Kelvins, so that electrode sample is kept 20min at a set temperature, the air pressure in reaction chamber is
30 millitorrs；
B. air outlet valve is opened, pulse cleans gas nitrogen, cleans 12s；
C. air outlet valve is closed, the mixture of pulsed gaseous trimethyl aluminium and two luxuriant magnesium, the time is 0.09 second, then keeps one
The section time 8 seconds；
D. air outlet valve is then opened, pulse cleans gas nitrogen, cleans 0.9 minute；Air outlet valve is closed, vacuumizes, removes more
Remaining byproduct of reaction；
E. it is then shut off air outlet valve, pulse hydrofluoric acid, the time is 8 seconds, then keeps a period of time 30s；
F. air outlet valve is then opened, pulse cleans gas argon gas, cleans 0.7 minute；It is again switched off air outlet valve, is vacuumized, is moved
Remove extra byproduct of reaction；
G. return step c, circulation execute c-f step.
The clad speed of growth is the every circulation of 1.18 Ethylmercurichlorendimides, and having been coated metal oxide thickness is about 600 Ethylmercurichlorendimides
Positive electrode material precursor.
Presoma after cladding is directly mixed with lithium source (lithium source may be, but is not limited to lithium hydroxide and lithium carbonate), so
Afterwards by sintering reaction, sintering temperature 250-1500 Kelvin, sintering time 8 hours, sintering atmosphere include but is not limited to vacuum,
Air, oxygen, argon gas realize that thermal expansion is scattered to inside positive electrode during the sintering process for the element of cladding, form doping type mangaic acid
Lithium.
Embodiment 8
A. by presoma bulk silica manganese MnO2Dusty material is placed in atomic layer deposition instrument reaction chamber, is vacuumized simultaneously
Reaction chamber temperature is heated to 1000 Kelvins, electrode sample is made to keep 15min at a set temperature, the air pressure in reaction chamber is 5
Millitorr；
B. air outlet valve is opened, pulse cleans gas nitrogen, cleans 6s；
C. air outlet valve, the mixture of pulsed gaseous trimethyl aluminium and hafnium acid tetra-isopropyl are closed, the time is 6 seconds, is then protected
Hold 25 seconds a period of times；
D. air outlet valve is then opened, pulse cleans gas nitrogen, cleans 0.3 minute；Air outlet valve is closed, vacuumizes, removes more
Remaining byproduct of reaction；
E. it is then shut off air outlet valve, pulse hydrogen sulfide, the time is 1 second, then keeps a period of time 40s；
F. air outlet valve is then opened, pulse cleans gas nitrogen, cleans 0.2 minute；It is again switched off air outlet valve, is vacuumized, is moved
Remove extra byproduct of reaction；
G. return step c, circulation execute c-f step.
The clad speed of growth is the every circulation of 1.09 Ethylmercurichlorendimides, coated metal oxide thickness be about 70 Ethylmercurichlorendimides just
Pole material precursor.
Presoma after cladding is directly mixed with lithium source (lithium source may be, but is not limited to lithium hydroxide and lithium carbonate), so
Afterwards by sintering reaction, sintering temperature 250-1500 Kelvin, sintering time 10 hours, sintering atmosphere was including but not limited to true
Sky, air, oxygen or argon gas realize that thermal expansion is scattered to inside positive electrode during the sintering process for the element of cladding, form doping type
LiMn2O4.
It should be noted last that the above specific embodiment is only used to illustrate the technical scheme of the present invention and not to limit it,
Although being described the invention in detail referring to preferred embodiment, those skilled in the art should understand that, it can be right
Technical solution of the present invention is modified or replaced equivalently, without departing from the spirit and scope of the technical solution of the present invention,
It is intended to be within the scope of the claims of the invention.
Claims (13)
1. a kind of anode material of lithium battery presoma with film nuclear structure, which is characterized in that including presoma ontology and uniformly
Be coated on the film of presoma body surface, the film be anode material of lithium battery doping metals or metal oxide or
Metal nitride or metal chloride or metal halide or metal fluoride or metal sulfide or III-V element
One or more of object or two or six group element compounds material are closed, is grown by atomic layer deposition method；The film is thick
Degree is 0.2 sodium rice to 1000 nanometers.
2. the anode material of lithium battery presoma according to claim 1 with film nuclear structure, which is characterized in that before described
Drive body bulk material is nickel cobalt manganese hydroxide (NixCoyMnz)OH2, cobaltosic oxide Co3O4, manganese dioxide MnO2, four oxidations
Three manganese Mn3O4Or FePO4。
3. the preparation method of the anode material of lithium battery presoma described in claim 1 with film nuclear structure, which is characterized in that
The following steps are included:
A. lithium battery anode presoma bulk powder material is placed in atomic layer deposition reaction chamber, heating reaction chamber temperature arrives
250~1000 Kelvins keep lithium battery anode presoma bulk powder material powder at such a temperature 1~1000 minute；
B. it is passed through cleaning gas, is cleaned 0~6000 minute；
C. gaseous precursor A or precursor A containing doped chemical are passed through and takes sparkling mixture, the time is 0.01~
10000 seconds, then keep 1 second~500 minutes a period of time；
D. it is passed through cleaning gas, cleans 0.1~1000 minute, removes extra byproduct of reaction；
E. precursor B or precursor B are passed through and takes sparkling mixture, the time is 0.01~10000 second, then keeps one section
Time 1 second~500 minutes；
F. it is passed through cleaning gas, cleans 0.1~1000 minute, removes extra byproduct of reaction；
G. circulation executes step c-f, until obtaining required 0.2 sodium rice of cladding thickness to 1000 nanometers.
4. the preparation method of the anode material of lithium battery presoma according to claim 3 with film nuclear structure, feature
It is, the clad speed of growth is the every circulation of 1 to 100 Ethylmercurichlorendimides, and a circular in definition is the step c to step f.
5. the preparation method of the anode material of lithium battery presoma according to claim 3 with film nuclear structure, feature
It is, before step a, the lithium battery anode presoma bulk powder material passes through O2, N2O,NO2, NH3, H2S, F2, HF,
N2, H2, the corona treatment of inert gas or above-mentioned gas, treatment temperature be 250~1200 Kelvins, the time be 0~
300 minutes.
6. the preparation method of the anode material of lithium battery presoma according to claim 3 with film nuclear structure, feature
It is, gas fluidized using mechanical oscillation or rotation during the step a-f, ultrasonic wave mode is anti-to atomic layer deposition
The lithium battery anode presoma bulk powder material in chamber is answered to implement grain fluidized, to realize uniform coated.
7. the preparation method of the anode material of lithium battery presoma according to one of claim 3 to 6 with film nuclear structure,
It is characterized in that, the precursor A selection is trimethyl aluminium, alchlor, tetraisopropyl titanate, titanium tetrachloride, hafnium acid four are different
Propyl ester, two luxuriant magnesium and sodium, calcium, zinc, magnesium, aluminium, iron, copper, yttrium, chromium, manganese, tungsten, silicon, titanium, zirconium, hafnium, lanthanum, tantalum, molybdenum, lithium, boron,
The mixing of one or more of phosphorus, the metallo-organic compound of fluorine, halide, alkoxide, metal p-diketonates complex compound, fluoride
Object.
8. the preparation method of the anode material of lithium battery presoma according to claim 7 with film nuclear structure, feature
It is, the precursor B is water, oxygen, ozone, hydrogen peroxide, plasma oxygen atom, ammonia, plasma nitrogen-atoms, plasma
Body hydrogen atom, hydrogen sulfide, fluorine gas, the mixture of one or several substances of hydrofluoric acid.
9. the preparation method of the anode material of lithium battery presoma according to claim 8 with film nuclear structure, feature
It is, the cleaning gas is nitrogen or argon gas；Carrying gas is nitrogen or argon gas.
10. the processing method of the anode material of lithium battery presoma as claimed in claim 1 or 2 with film nuclear structure, feature exist
In, the positive electrode material precursor is sintered, sintering temperature be 250-1500 Kelvin, sintering atmosphere be vacuum, air, oxygen
Or argon gas, sintering time are 1-24 hours, so that the thermal expansion in calcination process of the element of cladding is scattered to inside presoma, formation is mixed
Miscellaneous type presoma.
11. utilizing the doping type lithium battery anode material for the doping type precursor preparation that processing method described in claim 10 obtains
Material, which is characterized in that be sintered, sintering temperature 250-1500 Kelvin, be sintered after mixing the doping type presoma with lithium source
Time 1-24 hour, sintering atmosphere are vacuum, air, oxygen or argon gas, and making the element coated, thermal expansion is scattered to during the sintering process
Inside positive electrode, the doping type anode material of lithium battery is obtained.
12. utilizing the doping type lithium electricity of the anode material of lithium battery precursor preparation described in as claimed in claim 1 or 22 with film nuclear structure
Pond positive electrode, which is characterized in that directly mix the anode material of lithium battery presoma with film nuclear structure with lithium source
After be sintered, sintering temperature 250-1500 Kelvin, time 1-24 hour, sintering atmosphere is vacuum, air, oxygen or argon gas, real
Thermal expansion is scattered to inside positive electrode the element now coated during the sintering process, forms doping type anode material of lithium battery.
13. doping type anode material of lithium battery according to claim 4 or 5, which is characterized in that doped chemical include sodium,
Calcium, zinc, magnesium, aluminium, yttrium, iron, copper, chromium, tungsten, manganese, silicon, titanium, zirconium, hafnium, lanthanum, tantalum, molybdenum, lithium, boron, phosphorus, fluorine one of or it is several
The mixture of kind.
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