CN108448055A - Anode material for lithium-ion batteries and preparation method thereof - Google Patents
Anode material for lithium-ion batteries and preparation method thereof Download PDFInfo
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- CN108448055A CN108448055A CN201810200628.4A CN201810200628A CN108448055A CN 108448055 A CN108448055 A CN 108448055A CN 201810200628 A CN201810200628 A CN 201810200628A CN 108448055 A CN108448055 A CN 108448055A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
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- 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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The present invention relates to anode material for lithium-ion batteries and preparation method thereof.According to an embodiment, a kind of anode material for lithium-ion batteries may include：Positive electrode particle；And it is coated on the solid electrolyte film on the outer surface of the positive electrode particle, the solid electrolyte film is continuous film of thickness in the range of 1 50nm, the solid electrolyte film includes the amorphous phase and crystalline phase coexisted, crystallite dimension does not form new phase in the range of 1 40nm, and between the solid electrolyte film and the positive electrode particle.The anode material for lithium-ion batteries of the present invention can improve electrochemical stability, the problem of positive electrode particle volume expansion and transition metal can be inhibited to dissolve out simultaneously, therefore have many advantages, such as that electrochemical stability is high, cycle performance is good, structural stability is strong, high-voltage performance is good and safe.
Description
Technical field
Present invention relates in general to new energy fields, more specifically it relates to which a kind of surface coats nano-solid dielectric film
Anode material for lithium-ion batteries and preparation method thereof.
Background technology
The energy plays an important role in the evolution of modern society, and traditional fossil fuel is gradually not
The needs of global economy rapid development can be met, and fossil fuel can also bring environmental pollution and greenhouse effects, so being badly in need of
New clean energy resource is developed, such as：Solar energy, wind energy, tide energy and geothermal energy.However, these energy are over time and space
It is unstable, needs conversion that could utilize and store.Therefore, particularly urgent to the exploitation of stable clean energy resource.
Lithium ion battery has high-energy density, low self-discharge rate, wide use temperature range, long circulation life, environment friend
Good, memory-less effect and can be with high current charge-discharge the advantages that, become current most effective energy storage equipment, disappear in tradition
The numerous areas such as power-consuming son, electric tool, electronic traffic and energy-accumulating power station show boundless application prospect.
Demand with people to lithium ion battery with high energy density is constantly promoted, and improves lithium ion battery under high voltages
Electrochemical stability, become the important topic of industry research.And core material of the positive electrode as lithium ion battery, to electricity
The final performance in pond plays a crucial role, and the technology that the optimization of the performance of lithium ion battery often relies on positive electrode is prominent
It is broken.Anode material for lithium-ion batteries conventional at present under high voltages generally existing structure destroy, electrochemical stability reduce with
And transition metal the problem of dissolving out, so improving anode material for lithium-ion batteries structure under high voltages and electrochemical stability
It is just particularly important, commonplace way is to coat one layer of electrolyte on positive electrode surface.In research before, institute
The operation of use is by the presoma of electrolyte or will to be coated on positive electrode particle surface at the electrolyte after phase,
Using high-temperature calcination.However experiment is found, the positive electrode being prepared reduces traditional positive electrode to a certain extent
Performance, and effect is limited in terms of improving structural stability.
Therefore, still it is desirable to provide a kind of anode material for lithium-ion batteries and preparation method thereof, it can be in positive material
There is further improvement in terms of the performance and/or stability of material.
Invention content
The one side of the application is to provide a kind of anode material for lithium-ion batteries and preparation method thereof, can be into one
Step improves the performance and/or stability of positive electrode.
According to an exemplary embodiment, a kind of anode material for lithium-ion batteries is provided, including：Positive electrode particle；And
The solid electrolyte film being coated on the outer surface of the positive electrode particle, the solid electrolyte film are thickness in 1-50nm
In the range of continuous film, the solid electrolyte film includes the amorphous phase and crystalline phase coexisted, model of the crystallite dimension in 1-40nm
In enclosing, and new phase is not formed between the solid electrolyte film and the positive electrode particle.
In some instances, the positive electrode particle includes cobalt acid lithium, LiFePO4, LiMn2O4, ternary layered oxidation
Object, rich at least one of lithium and nickel ion doped, and the solid electrolyte film includes Li1+xAlxM2-x(PO4)3, wherein M is
Ti or Ge, 0≤x<0.7.
In some instances, the D50 granularities of the positive electrode particle are in the range of 1-25 μm, and solid electricity
The mass percent of plasma membrane is solved in the range of 0.01% to 10%.
According to another exemplary embodiment, a kind of preparation method of anode material for lithium-ion batteries is provided, including：Prepare just
Pole material granule；Solid electrolyte film is coated on the surface of positive electrode particle, the solid electrolyte film includes electrolyte
The presoma of material or the electrolyte of Cheng Xianghou；And the positive electrode particle for being coated with solid electrolyte film is carried out
Heating, heating temperature is in the range of 50-500 DEG C.
In some instances, the heating carries out in air or oxygen-containing atmosphere.
In some instances, pass through atomic layer deposition the step of coating solid electrolyte film on the surface of positive electrode particle
Area method, the precipitation method, pulsed laser deposition, evaporation, magnetron sputtering method, sol-gal process, chemical vapour deposition technique and hydro-thermal
At least one of method carries out.
In some instances, it is used in the precipitation method, the evaporation, the sol-gal process and the hydro-thermal method
Solvent include methanol, ethyl alcohol, propyl alcohol, ethylene glycol, benzyl alcohol, acetic acid, N-Methyl pyrrolidone, acetone, acetonitrile, tetrahydrofuran,
In dimethyl carbonate, propene carbonate, benzene,toluene,xylene, methyl ether, ether, glycol dimethyl ether and deionized water at least
It is a kind of.
According to another exemplary embodiment, a kind of lithium battery, including anode are provided, the anode includes above-mentioned lithium-ion electric
Pond positive electrode.
In some instances, the lithium battery includes liquid lithium ionic cell, mixing solid-liquid lithium ion battery, mixing solid-liquid
Lithium metal battery, all-solid lithium-ion battery and all solid state lithium metal battery.
In some instances, when the positive electrode particle includes cobalt acid lithium, the charge cutoff voltage of the lithium battery
It is about 4.6V, when the positive electrode particle includes LiFePO4, the charge cutoff voltage of the lithium battery is about
3.7V, when the positive electrode particle includes LiMn2O4, the charge cutoff voltage of the lithium battery is about 4.3V, when described
When positive electrode particle includes ternary layered oxide, the charge cutoff voltage of the lithium battery is about 4.6V, when it is described just
When pole material granule includes rich lithium, the charge cutoff voltage of the lithium battery is about 4.9V, and works as the positive electrode particle
When including nickel ion doped, the charge cutoff voltage of the lithium battery is about 5.0V.
Compared with prior art, anode material for lithium-ion batteries provided by the invention and preparation method thereof at least has as follows
Advantage：
First, the preparation sintering temperature of the material at 500 DEG C hereinafter, between solid electrolyte particle film and positive electrode particle
It will not react and form new phase；
Furthermore, it is possible to form thin continuous film outside positive electrode particle, to realize good cladding, electricity has been alleviated or avoided
Solve the reunion accumulation of matter island；
In addition, the positive electrode of this structure can ensure while lithium ion normally transports, to effectively prevent electrolyte
With being in direct contact for anode, the problem of inhibiting positive electrode particle volume expansion and transition metal to dissolve out, therefore be substantially improved lithium from
While sub- battery energy density, cyclical stability and structural stability of the positive electrode under high working voltage can be promoted,
Have many advantages, such as that high-voltage performance is good and safe；
Furthermore the method for the manufacture anode material for lithium-ion batteries of the application is simple and practicable, is readily applied to extensive life
In production.
The above and other feature and advantage of the present invention will be from below in conjunction with the accompanying drawings becoming the description of exemplary embodiment
It obtains obviously.
Description of the drawings
Fig. 1 is the structural schematic diagram of anode material for lithium-ion batteries according to an embodiment of the invention；
Fig. 2 is the flow chart of manufacture anode material for lithium-ion batteries according to an embodiment of the invention；
Fig. 3 A are the transmission electron microscope picture before being recycled according to the LCO of one embodiment of the invention；
Fig. 3 B are the transmission electron microscope picture after being recycled 50 weeks according to the LCO of one embodiment of the invention；
Fig. 4 is the variation that 50 weeks specific discharge capacities are recycled according to the LCO of the different LATP covering amounts of one embodiment of the invention
Curve；
Fig. 5 is metallic lithium surface Co2p after being recycled 50 weeks according to the LCO of the different LATP covering amounts of one embodiment of the invention
X-ray photoelectron spectroscopic analysis figure；
Fig. 6 is to be recycled 50 weeks according to the LCO of the LCO and uncoated LATP of the cladding 0.5%LATP of one embodiment of the invention
The comparison diagram of capacity；And
Fig. 7 is not wrap according to the LCO of the cladding 0.5%LAGP of one embodiment of the invention, the LCO of cladding 1.5%LAGP and
The LCO for covering LAGP recycles the comparison diagram of 50 weeks specific discharge capacities.
Specific implementation mode
In the following with reference to the drawings and specific embodiments, the application is described in more detail.It should be understood that described
Embodiment is only a part of the embodiment of the application, and the application is not limited to these embodiments described herein.
Fig. 1 is the structural schematic diagram of anode material for lithium-ion batteries 100 according to an embodiment of the invention.As shown in Figure 1,
Anode material for lithium-ion batteries 100 includes that positive electrode particle 110 and the nanometer being coated on the surface of positive electrode particle are solid
Body electrolyte granular film 120.It should be understood that although Fig. 1 shows circular granular, anode material for lithium-ion batteries 100
There can be irregular grain shape.Solid electrolyte particle film 120 can be one layer of continuous fine and close nanostructure, cladding
Positive electrode particle 110.The numerous characteristics of anode material for lithium-ion batteries 100 will be described in conjunction with preparation method below.
Fig. 2 is the flow chart of manufacture anode material for lithium-ion batteries according to an embodiment of the invention.As shown in Fig. 2, side
Method 200 may begin at step S210, prepare positive electrode particle 110.Positive electrode particle 110 may include any existing or future
The positive electrode of exploitation, example include but not limited to such as cobalt acid lithium, LiFePO4, LiMn2O4, ternary layered oxide, richness
Lithium and nickel ion doped etc..Positive electrode particle 110 may include one or more in these materials.In some instances, just
The D50 granularities of pole material granule 110 can be in such as 1~25 μm of range.
Next, in step S220, solid electrolyte film can be coated on the outer surface of positive electrode particle 110
120.Here, the solid electrolyte film 120 coated can be the presoma of electrolyte, can also be into electrolysis after phase
Material.Presoma can react during cladding and in the heating process that is described below, final to generate
Electrolyte.The example of solid electrolyte material may include but be not limited to Li1+xAlxM2-x(PO4)3, wherein M can be Ti
Or Ge, 0≤x ＜ 0.7.The mass percent of solid electrolyte film 120 can be in the range of 0.01% to 10%.
Encapsulation steps S220 can be carried out by various methods, example include but not limited to atomic layer deposition method, the precipitation method,
Pulsed laser deposition, evaporation, magnetron sputtering method, sol-gal process, chemical vapour deposition technique and hydro-thermal method etc..It is heavy when taking
When shallow lake method, evaporation, sol-gal process and hydro-thermal method, wherein used solvent may include but be not limited to methanol, ethyl alcohol, third
Alcohol, ethylene glycol, benzyl alcohol, acetic acid, N-Methyl pyrrolidone, acetone, acetonitrile, tetrahydrofuran, dimethyl carbonate, propylene carbonate
Ester, benzene,toluene,xylene, methyl ether, ether, glycol dimethyl ether and deionized water etc..These methods are all people in the art
Known to member, therefore its specific steps is not detailed herein.
Then in step S230, the positive electrode particle 110 for being coated with solid electrolyte film 120 can be added
Heat.Heating can be such that solid electrolyte material presoma fully reacts to generate solid electrolyte material, and can promote solid
Well contacting between body dielectric film and positive electrode particle.Heating can carry out in air, can also be suitable at other
Atmosphere such as oxygen-containing atmosphere in carry out.
In the heating stepses that the past executes, the contact in order to make electrolyte uniformly coat, and between electrode
More preferably, heating temperature is generally at 600 DEG C or more.However, the inventors discovered that, the heating of such high-temperature, which is be easy to cause, to be electrolysed
It reacts between matter and electrode material and generates one layer of passivation layer, the performance of positive electrode can be reduced instead.Moreover, such
Heating process causes electrolyte to reunite on positive electrode particle surface than more serious, the multiple discrete island structures of formation, therefore not
The effect that protection structural stability can effectively be played, inhibit transition metal dissolution.
In order to slow down or avoid these problems, in step S230, heating can be carried out in 500 DEG C of temperature below, example
It can such as be carried out at a temperature of between 50-500 DEG C.By the heating in the temperature range, the solid electrolyte film that is generated
120 include the coexisting phase of amorphous phase and crystalline phase, and the crystallite dimension of crystalline phase is in the range of 1-40nm.Since heating temperature is relatively low,
New phase, i.e., no passivation layer are not formed between solid electrolyte film 120 and positive electrode particle 110.The present inventor is also
It was found that the heating of this lower temperature also greatly reduces agglomeration, solid electrolyte film 120 can be formed as continuously causing
Close film, and it can be ultra-thin film, and film thickness can be in the range of 1-50nm.Even if being formed as film thin in this way, due to
Reduce reunion, can still realize good cladding to positive electrode particle 110.Therefore, the positive electrode 100 of this structure
It can ensure while lithium ion normally transports, electrolyte is effectively prevent to be in direct contact with positive, inhibit positive electrode particle body
The problem of product expansion and transition metal dissolution, to while lithium ion battery energy density is substantially improved, be promoted just
Cyclical stability and structural stability of the pole material under high working voltage have many advantages, such as that high-voltage performance is good and safe.
Moreover, the method for the manufacture anode material for lithium-ion batteries of the present invention is simple and practicable, it is readily applied in large-scale production.
Positive electrode 100 manufactured as above can be also used for that positive plate is made, and can be used for manufacturing lithium battery.It is described below
It manufactures positive electrode 100 and uses it to some specific embodiments for preparing lithium battery.It should be understood that providing these embodiments only
For enabling those skilled in the art to implement the present invention, rather than limit the scope of the invention in any way.
Embodiment 1
With the method for atomic layer deposition Li is coated on traditional positive electrode particle surface1.4Al0.4Ti1.6(PO4)3(LATP) thin layer：
On substrate by the tiling of 1g tradition positive electrode particles, with the raw material Li of LATP2CO3、Al2O3、TiO2And NH4H2PO4For target, true
Reciprocal of duty cycle is 10-2Under torr, voltage 24V, Ar atmosphere, deposit 28 seconds, 8 seconds, 64 seconds and 12 seconds respectively, by different starting materials
In traditional positive electrode surface, the powder of deposition is taken out later, is burnt 3 hours with 450 DEG C of temperature in air, you can obtain
LCoO2(LCO) positive pole powder of the 0.2%LATP coated on.
The LCO particles that above-mentioned surface is coated with to LATP dress up the lithium metal battery of liquid electrolyte.Specifically：By surface
The LCO particles of LATP are coated with Super P, binder PVDF according to 8:1:1 mass ratio mixing, is added suitable solvent
NMP is ground into uniform slurry, scratches on aluminium foil, pole piece of the backlash at a diameter of 14mm is dried, in 120 DEG C of baking oven
After vacuum drying 10 hours, it is transferred in the glove box full of Ar atmosphere；Using lithium metal as cathode, 1M LiPF6It is dissolved in EC/DMC
(ethylene carbonate/methyl carbonate) (volume ratio 1:1) it is used as electrolyte, with celgard films (PP/PE/PP) for diaphragm, assembly
At CR2032 button cells.
Battery made of above-mentioned can use constant current charge-discharge pattern to carry out electrochemical property test, and electric discharge is by voltage
3.0V, charging are 4.5V by voltage, and all tests carry out under the current density of 0.2C.After circulating battery 50 weeks,
It tears battery in glove box open, rinses metallic lithium surface five times with DMC (dimethyl carbonate), drained in transitional storehouse, detect lithium metal
The peaks Co 2p on surface, to judge the case where positive electrode particle transition metal dissolves out.
The LCO particles that above-mentioned surface is coated with to LATP dress up polymer metal lithium battery.The specific steps are：By PEO and
LiTFSI (molar ratio EO/Li=15) is dissolved in acetonitrile, after stirring 5 hours, by obtained slurry blade coating on centrifugation paper,
It is dried in vacuo 24 hours in 45 DEG C of baking oven, is washed into the disk of diameter 16.2mm, centrifugation paper is torn and can be obtained PEO electrolysis
Matter.It is 85 that surface, which is coated with the LCO particles of LATP, carbon nanotube, PEO, LiTFSI according to mass ratio,:2:12:1 mixing, adds
Enter suitable NMP, blade coating is dried in vacuo 12 hours in 60 DEG C of baking oven, is washed into a diameter of on Al foils after stirring evenly
The pole piece of 14mm；Using lithium metal as cathode, PEO is electrolyte, is assembled into CR2032 button cells.Battery can be with made of above-mentioned
Electrochemical property test is carried out using constant current charge-discharge pattern, electric discharge is 3.0V by voltage, and charging is 4.2V, institute by voltage
There is test to be carried out under the current density of 0.2C.
Embodiment 2
With the precipitation method LATP thin layers are coated on traditional positive electrode particle surface：8g tradition anodes are dispersed in 300ml acetonitriles,
It is stirred 1 hour in beaker, the raw material Li of LATP is added2CO3(0.011g),Al2O3(0.0041g)、TiO2(0.026g) and
NH4H2PO4(0.07g) after stirring 3 hours, stops stirring, and propyl alcohol is added as settling agent, later, by sediment at 120 DEG C
It is dried in vacuo in baking oven 12 hours, is finally burnt 3 hours with 480 DEG C of temperature in air, you can obtain the anode of cladding LATP
Powder.
The positive electrode particle that cladding obtains is prepared into the lithium metal battery and polymer metal lithium battery of liquid electrolyte, tool
Body step is as the method for assembling battery in embodiment 1, and details are not described herein again.
Embodiment 3
With pulsed laser deposition LATP thin layers are coated on traditional positive electrode particle surface：1g tradition positive electrode particles are layered on lining
On bottom, with the raw material Li of LATP2CO3、Al2O3、TiO2And NH4H2PO4For target, cooling water is connected, vacuum degree 10 is being extracted into- 2When torr or less, it is passed through O2As protective atmosphere, by the deposition number of plies of these types of raw material be set to 28 layers, 8 layers, 64 layers and
12 layers, after deposition is completed, powder is taken out, burnt 3 hours with 450 DEG C of temperature in air, you can obtains cladding LATP's
Positive pole powder.
The positive electrode particle that cladding obtains is prepared into the lithium metal battery and polymer metal lithium battery of liquid electrolyte, tool
Body step is as the method for assembling battery in embodiment 1, and details are not described herein again.
Embodiment 4
With evaporation LATP thin layers are coated on traditional positive electrode particle surface：LATP powder is prepared first, by Li2CO3
(1.0862g)、Al2O3(0.4119g)、TiO2(2.5815g) and NH4H2PO4(6.9715g) is mixed, and suitable acetone is added and makees
For dispersant, with 350r/min ball millings 5 hours, later, the slurry that ball milling obtains is dried in 100 DEG C of baking oven, finally
The powder arrived is burnt 5 hours at 900 DEG C, you can obtains Li1.4Al0.4Ti1.6(PO4)3(LATP) powder；Secondly, the LATP that will be obtained
Powder is put into high-energy ball milling tank, and suitable acetonitrile is added, and with the speed high-energy ball milling 5 hours of 1800r/min, obtains nanoscale
LATP acetonitrile slurries；Again, 3g tradition positive pole powders are taken to be dispersed in 150ml acetonitriles, stirring 1 is small in beaker at room temperature
When, the nanoscale LATP glues (the wherein LATP containing 0.03g) that will be dispersed in acetonitrile are added thereto, and are stirred and are steamed at 60 DEG C
It is dry, it is 15 hours dry in 120 DEG C of baking oven；Finally, it burns 3 hours at 480 DEG C in air, you can obtaining cladding LATP just
Pole powder.
The positive electrode particle that cladding obtains is prepared into the lithium metal battery and polymer metal lithium battery of liquid electrolyte, tool
Body step is as the method for assembling battery in embodiment 1, and details are not described herein again.
Embodiment 5
With magnetron sputtering method LATP thin layers are coated on traditional positive electrode particle surface：Plated film is added in 1g tradition positive pole powders
Room, with the raw material Li of LATP2CO3、Al2O3、TiO2And NH4H2PO4For target 10 are extracted into vacuum degree using Ar as protective atmosphere- 2When torr or less, applies 280K DC voltages, the raw material of LATP is sputtered at into traditional positive electrode particle surface, the sputtering of raw material
Duration is set to 30 seconds, 10 seconds, 40 seconds, 8 seconds, and sputtering takes out powder after completing, and burns 3 hours at 480 DEG C in air, i.e.,
It can obtain the positive pole powder of cladding LATP.
The positive electrode particle that cladding obtains is prepared into the lithium metal battery and polymer metal lithium battery of liquid electrolyte, tool
Body step is as the method for assembling battery in embodiment 1, and details are not described herein again.
Embodiment 6
With sol-gal process LATP thin layers are coated on traditional positive electrode particle surface：3g tradition anodes are dispersed in 150ml
In ionized water, is stirred 1 hour in beaker under room temperature, the raw material Li of LATP is added2CO3(0.011g)、Al2O3
(0.0041g)、TiO2(0.026g) and NH4H2PO4(0.07g) is stirred at 80 DEG C and is evaporated, later, in 120 DEG C of baking oven
Vacuum drying 12 hours is finally burnt 3 hours at 480 DEG C, you can the positive pole powder coated in air.
The positive electrode particle that cladding obtains is prepared into the lithium metal battery and polymer metal lithium battery of liquid electrolyte, tool
Body step is as the method for assembling battery in embodiment 1, and details are not described herein again.
Embodiment 7
With laser induced chemical vapor depostion method LATP thin layers are coated on traditional positive electrode particle surface：2g tradition positive pole powders are spread
On substrate, with the raw material Li of LATP2CO3(0.011g),Al2O3(0.0041g)、TiO2(0.026g) and NH4H2PO4(0.07g)
For target, 10 are extracted into using Ar as protective atmosphere, in vacuum degree-2When torr or less, basal plate preheating temperature is set as 500 DEG C, laser
Power is that 150W is deposited, and after deposit, obtained powder is taken out, with 450 DEG C of temperature burning 3 hours in air, i.e.,
It can obtain the positive pole powder of cladding LATP.
The positive electrode particle that cladding obtains is prepared into the lithium metal battery and polymer metal lithium battery of liquid electrolyte, tool
Body step is as the method for assembling battery in embodiment 1, and details are not described herein again.
Embodiment 8
With hydro-thermal method LATP thin layers are coated on traditional positive electrode particle surface：By raw material Li OH (0.024g), the Al of LATP2O3
(0.04g)、TiO2(0.026g) and (NH4)3PO4(0.07g) is added in 200ml ammonium hydroxide, with the speed ball milling 5h of 350r/min,
The slurry that ball milling obtains is quickly transferred in water heating kettle, and 3g tradition positive pole powders are added, 12 are kept the temperature in 260 DEG C of baking oven
Hour, by slurries filtration, obtained solid is dried in vacuo 5 hours in 80 DEG C of baking oven, is burnt in air with 480 DEG C of temperature
3 hours, you can obtain the positive pole powder of cladding LATP.
The positive electrode particle that cladding obtains is prepared into the lithium metal battery and polymer metal lithium battery of liquid electrolyte, tool
Body step is as the method for assembling battery in embodiment 1, and details are not described herein again.
The positive electrode particle that Examples 1 to 8 coats can not only be assembled into liquid metal lithium battery and polymer metal
Lithium battery can be applied in remaining battery system.Embodiment 9~80 shown in following table 1 is the difference that cladding obtains
The blanking voltage that the applicable battery system of positive electrode and highest can fill.
Table 1
Fig. 3 A are the cladding 0.5%Li according to one embodiment of the invention1.4Al0.4M1.6(PO4)3(LATP) LCoO2(LCO)
Transmission electron microscope picture before cycle.Fig. 3 B are the LCO according to the cladding 0.5%LATP of one embodiment of the invention in liquid electrolyte
In lithium metal battery, when charge cutoff voltage is 4.5V, transmission electron microscope picture of the cycle after 50 weeks.By the transmission electricity of Fig. 3 A and Fig. 3 B
Mirror figure compares as can be seen that LATP electrolyte forms one layer of very thin continuous film in positive electrode surface, and dielectric film is by amorphous and receives
The brilliant composition of rice.After recycling 50 weeks under charge cutoff voltage is the high voltage of 4.5V, continuous film still remains, and illustrates this layer of electricity
Solution plasma membrane plays the role of that positive electrode particle and electrolyte is isolated really, prevents the reaction of active particle and electrolyte, ensure that
The structural stability of active particle；The contact that also demonstrates between active particle and dielectric film simultaneously is relatively good, there is no because
It falls off for the multiple charge and discharge of battery.Moreover, can be seen that first all discharge capacities up to 180mAh/g, first week from charging and discharging curve
Coulombic efficiency is about 98%, and charge and discharge potential plateau is about 4.0V, and after circulating battery 50 weeks, discharge capacity is still reachable
160mAh/g, coulombic efficiency are about 96%.The present inventor is also to the LCO of the cladding 0.5%LATP of another embodiment in PEO bases
Charge and discharge cycles test, charge cutoff voltage 4.2V, first week discharge capacity have been carried out in all solid state lithium metal battery of polymer
For 125mAh/g, and there was only few decaying 50 weeks later.Therefore, have using the lithium battery of the positive electrode of the present invention
Good cyclical stability.
Fig. 4 is LCO (0%LATP LCO, the 0.2%LATP according to the different LATP covering amounts of one embodiment of the invention
LCO, 0.5%LATP@LCO, 1%LATP@LCO, 1.5%LATP@LCO) in the lithium metal battery of liquid electrolyte, charging is cut
When only voltage is 4.5V, the variation of 50 weeks specific discharge capacities is recycled.As can be seen that being coated with the LCO materials of LATP with cycle
Number is continuously increased, and capacity does not have apparent decaying, and uncoated LCO is then as cycle-index increases decaying significantly.
As it can be seen that LATP films effectively prevent LCO particles to be in direct contact under high voltages with electrolyte, and then both inhibit anti-
It answers, the structure and chemical property of stabilizing active particle.
Fig. 5 is LCO (0%LATP LCO, the 0.2%LATP according to the different LATP covering amounts of one embodiment of the invention
LCO, 0.5%LATP@LCO, 1%LATP@LCO, 1.5%LATP@LCO) in the lithium metal battery of liquid electrolyte, charging is cut
When only voltage is 4.5V, the X-ray photoelectron spectroscopic analysis figure of metallic lithium surface Co 2p after cycle 50 weeks.Pass through X-ray photoelectricity
The content of metallic lithium surface transition metal Co after sub- energy spectrum analysis detection recycles in the lithium metal battery of liquid electrolyte, can
To find out, the positive electrode particle after all claddings is after circulating battery 50 weeks, and in metallic lithium surface, there is no transition metal Co 2p
Peak, and the positive electrode particle of uncoated dielectric film is in 50 weeks characteristic peaks for having Co 2p later of circulating battery.It is possible thereby to illustrate this
The positive electrode that the continuous dense film of kind coats effectively can inhibit transition metal to dissolve out, and play the role of rock-steady structure.
Fig. 6 is poly- in PEO bases according to the LCO of the LCO and uncoated LATP of the cladding 0.5%LATP of one embodiment of the invention
When charge cutoff voltage is 4.2V in all solid state lithium metal battery of conjunction object, the change curve of 50 weeks specific discharge capacities is recycled.It can
To find out the LCO of cladding 0.5%LATP after 50 weeks cycles, specific discharge capacity only has a small amount of decaying, and uncoated LATP
LCO cycle 12 weeks after capacity decayed to original 35%.This illustrates one layer of very thin LATP of LCO particle surfaces cladding
Film can prevent being in direct contact for positive electrode particle and organic polyelectrolyte, to prevent active particle to organic polymer electricity
Solve the oxidation of matter.
Fig. 7 is not wrap according to the LCO of the cladding 0.5%LAGP of one embodiment of the invention, the LCO of cladding 1.5%LAGP and
50 weeks specific discharge capacities of cycle when covering the LCO of LAGP charge cutoff voltage being 4.6V in the lithium metal battery of liquid electrolyte
Curve comparison.As can be seen that being coated with LCO materials being continuously increased with cycle-index of LAGP, capacity does not have significantly
Decaying, and pure phase LCO illustrates that LAGP films effectively prevent LCO under high voltages then as cycle-index increases decaying significantly
With being in direct contact for electrolyte, the structure and chemical property of positive electrode particle are stablized in and then the reaction both inhibited.
The anode material for lithium-ion batteries and preparation method thereof of cladding nano-solid dielectric film in surface provided by the invention,
It is to coat one layer continuously by the dense electrolyte plasma membrane of amorphous phase and nanocrystalline phase composition, the thickness of film in conventional cathode material surface
Degree is between 1-50nm, and the size of nanocrystal is between 1-40nm.As described above, pure positive active particles are under high voltages
It reacts with electrolyte, reduces the chemical property of battery.It is swollen volume to occur for positive electrode particle in charge and discharge process
It is swollen, and have the precipitation of transition elements, cause structure to be destroyed.And LAMP coated lithium ion battery anode materials are used in the present invention
It is coated on just by material since LAMP (M=Ti or Ge) itself has relatively high lithium ion conducting rate with uniform film-form
Pole particle surface is similar to and forms one layer of solid electrolyte interface layer (SEI), and lithium ion normally migrates, and but can directly separate
Being in direct contact for active particle and electrolyte, hinders active particle and is reacted with electrolyte, electrochemical stability is made to be improved；
Meanwhile lower treatment temperature (being less than 500 DEG C) will not make active particle and dielectric film react and generate new phase；This
Outside, this layer of dielectric film can also effectively inhibit positive electrode particle volume expansion and the dissolution of transition metal, play the work of rock-steady structure
With.
Above-described specific implementation mode has carried out further the purpose, technical solution and advantageous effect of the application
It is described in detail, it should be understood that the foregoing is merely the specific implementation mode of the application, is not intended to limit the present invention
Protection domain, all within the spirits and principles of the present invention, any modification, equivalent substitution, improvement and etc. done should all include
Within protection scope of the present invention.
Claims (10)
1. a kind of anode material for lithium-ion batteries, including：
Positive electrode particle；And
The solid electrolyte film being coated on the outer surface of the positive electrode particle, the solid electrolyte film are thickness in 1-
Continuous film in the range of 50nm, the solid electrolyte film include the amorphous phase and crystalline phase coexisted, and crystallite dimension is in 1-40nm
In the range of, and do not form new phase between the solid electrolyte film and the positive electrode particle.
2. anode material for lithium-ion batteries according to claim 1, wherein the positive electrode particle include cobalt acid lithium,
LiFePO4, LiMn2O4, ternary layered oxide, rich at least one of lithium and nickel ion doped, and the solid electrolyte
Film includes Li1+xAlxM2-x(PO4)3, wherein M is Ti or Ge, 0≤x<0.7.
3. anode material for lithium-ion batteries according to claim 1, wherein the D50 granularities of the positive electrode particle exist
In the range of 1-25 μm, and the mass percent of the solid electrolyte film is in the range of 0.01% to 10%.
4. a kind of preparation method of anode material for lithium-ion batteries, including：
Prepare positive electrode particle；
Solid electrolyte film is coated on the surface of positive electrode particle, before the solid electrolyte film includes electrolyte
Drive body or the electrolyte of Cheng Xianghou；And
Positive electrode particle to being coated with solid electrolyte film heats, and heating temperature is in the range of 50-500 DEG C.
5. according to the method described in claim 4, wherein, the heating carries out in air or oxygen-containing atmosphere.
6. according to the method described in claim 4, wherein, the step of solid electrolyte film is coated on the surface of positive electrode particle
Suddenly pass through atomic layer deposition method, the precipitation method, pulsed laser deposition, evaporation, magnetron sputtering method, sol-gal process, chemical gas
At least one of phase sedimentation and hydro-thermal method carry out.
7. according to the method described in claim 6, wherein, the precipitation method, the evaporation, the sol-gal process and described
The solvent used in hydro-thermal method include methanol, ethyl alcohol, propyl alcohol, ethylene glycol, benzyl alcohol, acetic acid, N-Methyl pyrrolidone, acetone,
It acetonitrile, tetrahydrofuran, dimethyl carbonate, propene carbonate, benzene,toluene,xylene, methyl ether, ether, glycol dimethyl ether and goes
At least one of ionized water.
8. a kind of lithium battery, including anode, the positive lithium ion battery including described in any one of claim 1-3 is just
Pole material.
9. lithium battery according to claim 8, wherein the lithium battery includes liquid lithium ionic cell, mixing solid-liquid lithium
Ion battery, mixing solid-liquid lithium metal battery, all-solid lithium-ion battery and all solid state lithium metal battery.
10. lithium battery according to claim 8, wherein when the positive electrode particle includes cobalt acid lithium, the lithium electricity
The charge cutoff voltage in pond is about 4.6V,
When the positive electrode particle includes LiFePO4, the charge cutoff voltage of the lithium battery is about 3.7V,
When the positive electrode particle includes LiMn2O4, the charge cutoff voltage of the lithium battery is about 4.3V,
When the positive electrode particle includes ternary layered oxide, the charge cutoff voltage of the lithium battery is about
4.6V
When the positive electrode particle includes rich lithium, the charge cutoff voltage of the lithium battery is about 4.9V, and
When the positive electrode particle includes nickel ion doped, the charge cutoff voltage of the lithium battery is about 5.0V.
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Application publication date: 20180824 |