CN110534706A - A kind of passivation of lithium powder and its preparation method and application - Google Patents
A kind of passivation of lithium powder and its preparation method and application Download PDFInfo
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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Abstract
The present invention provides a kind of passivation of lithium powder and its preparation method and application, belong to technical field of lithium ion.The preparation method of passivation of lithium powder provided by the invention, comprising the following steps: using lithium salts as electrolyte, using lithium piece as anode, using inert metal as cathode, be electroplated under the conditions of existing for the organic solvent and fluorochemical, obtain passivation of lithium powder.It is placed 1 month in the air below of humidity 20% using passivation of lithium powder prepared by method provided by the invention, significant change does not occur for the structure of passivation of lithium powder；For the prelithiation of graphite cathode and silicon-carbon cathode/benefit lithium, head circulation coulombic efficiency be can be improved to 99.8% or more；The graphite cathode and silicon-carbon cathode and LiCoO of prelithiation2Full battery head circulation coulombic efficiency Deng anode assembling can be improved to 98% or more, and low energy consumption, easy to operate and can continuously prepare, and is suitable for mass production.
Description
Technical field
The present invention relates to technical field of lithium ion, and in particular to a kind of passivation of lithium powder and its preparation method and application.
Background technique
Lithium ion battery has many advantages, such as that voltage is high, specific energy is high, has a safety feature, and has been widely used in portable electric
Sub- product and electric vehicle.The cathode of commercial lithium-ion batteries is mainly graphite and silicon carbon material at present.However, graphite and silicon-carbon
The intercalation potential of material is lower than ethylene carbonate (EC), the propene carbonate (PC), dimethyl carbonate (DMC), carbon in electrolyte
The reduction potential of the organic solvents such as diethyl phthalate (DEC), therefore these solvents can be reduced in negative terminal surface during the charging process
Generate one layer of solid electrolyte film (SEI) being made of lithia, lithium fluoride and organic lithium salt compound etc..The generation of SEI
Journey not only has electronics participation, it is necessary to and there is lithium ion to participate in reaction, it is initial due to graphite in lithium ion battery and silicon-carbon cathode
State is free of lithium, so that the formation of SEI need to consume the lithium ion of anode, positive-active lithium ion is caused to lose (7~15wt%),
Reduce battery energy density.
For this problem, prelithiation/benefit lithium technique is mainly taken to reduce the loss of positive-active lithium, i.e., in graphite or silicon-carbon
Active lithium is added in cathode, and compensation cathode forms the lithium of SEI consumption, avoids the loss of positive-active lithium.Cathode mends lithium technique at present
Mainly there is chemistry to mend lithium and electrochemistry and mend the methods of lithium, wherein not needed using lithium powder as the chemistry benefit lithium for mending lithium agent additional pre-
Assembly and disassembly process, it is high with lithium ion battery assembling process flow compatibility, it is very effective and mends lithium means.
Currently, the preparation method of lithium powder mainly continues to use strength mechanical shearing " microemulsified " method of FMC Corp.'s report, in conjunction with
The passivation of lithium powder of surface passivation technology preparation.For example, United States Patent (USP) US Pat.No.5776369 is disclosed to be had with inertia higher boiling
Solvent is protection solvent, and (> 200 DEG C) melt lithium metal at relatively high temperatures, the high shear force generated by high-speed stirred
Make molten metal lithium " microemulsified ", passivation additives are added, obtain passivation of lithium powder；Chinese patent CN 104393267A is also reported
Similar preparation method.However high-speed stirring apparatus and heating are needed by the method that mechanical shearing " microemulsified " prepares lithium powder
Device, degree that the device is complicated is high, and obtained passivation of lithium powder size is usually larger (tens arrive thousands of microns), large scale passivation of lithium powder
Increase the evenly dispersed difficulty of prelithiation process lithium powder.
Summary of the invention
The purpose of the present invention is to provide a kind of passivation of lithium powder and its preparation method and application.Preparation side provided by the invention
The passivation of lithium powder of method preparation has core-shell structure, and size is small, stable structure, and cycle performance is high；Low energy consumption for preparation method, easy to operate
And it can continuously prepare.
In order to achieve the above-mentioned object of the invention, the present invention the following technical schemes are provided:
The present invention provides a kind of preparation methods of passivation of lithium powder, comprising the following steps: using lithium salts as electrolyte, with lithium piece
For anode, using inert metal as cathode, it is electroplated under the conditions of existing for the organic solvent and fluorochemical, obtains passivation of lithium
Powder.
Preferably, the lithium salts includes LiPF6、LiAsF6, one or more of LiTFSI and LiFSI.
Preferably, the fluorochemical includes fluorinated ethylene carbonate and/or ammonium fluoride；
The organic solvent includes ether organic solvent or carbonate based organic solvent.
Preferably, the amount ratio of the lithium salts, fluorochemical and organic solvent be (0.8~1.5) mmol:(0.05~
0.3) mmol:1mL.
Preferably, the current density of the plating is 0.01~2.0mAcm-2, electroplating time is 0.25~8h.
Preferably, after the completion of the plating, further include gained passivation of lithium powder film is successively cleaned, ultrasound removing and dry
It is dry.
Preferably, the ultrasound removing carries out in atent solvent, and the atent solvent includes cyclic ether 1,3- dioxy penta
Ring, N-Methyl pyrrolidone, tetrahydrofuran, dimethyl carbonate or diethyl carbonate；It is described ultrasound removing time be 10~
30min。
The present invention provides preparation method described in above-mentioned technical proposal preparation passivation of lithium powder, the passivation of lithium powder be with
The spherical shape of nucleocapsid structure, wherein the core of nucleocapsid structure is formed by metallic lithium powder, and the shell of nucleocapsid structure is by lithium fluoride/oxygen
Change lithium compound to be formed.
Preferably, the size of the passivation of lithium powder is 0.3~4.0 μm, the shell thickness of the passivation of lithium powder is 10~
50nm。
The present invention also provides the passivation of lithium powder of the preparation of preparation method described in above-mentioned technical proposal or above-mentioned technical proposal institutes
Application of the passivation of lithium powder stated in lithium ion battery.
Passivation of lithium powder, preparation method thereof provided by the invention is easy to operate, does not need high-speed stirred and heating equipment, only need to be
Ultra-fine passivation of lithium powder can be prepared at room temperature, economize on resources, reduce production cost.Passivation of lithium powder prepared by the present invention
With nucleocapsid structure, wherein the shell structurre consistency that lithium fluoride/lithium oxide composite is formed is high, hinders moisture in air
It to the corrosiveness of lithium core, be stabilized passivation of lithium powder can in air of the humidity lower than 20%, and due to lithium metal
Fusing point is lower (455K), and room temperature has reached the 65% of fusing point, the pressure of stress caused by lithium diffusion, SEI film in electroplating process
Stress and electrolyte make lithium metal that creep occur the surface tension of lithium metal, become the engineering properties of class I liquid I, suitable shape
Make the regular spherical shape of lithium powder ultimately formed at mechanism, size is tens micron-sized much smaller than mechanical shearing " microemulsified "
Passivation of lithium powder makes to be easier to be uniformly dispersed when prelithiation, improves prelithiation effect.Passivation of lithium powder prepared by the present invention is used for stone
When the prelithiation of black cathode and silicon-carbon cathode, obtained prelithiation graphite cathode pole piece and silicon-carbon cathode pole piece is with 1mol/L's
LiPF4With in the electrolyte of the LiTFSI (solvent is EC:DEC:DMC volume ratio=1:1:1) of 1mol/L use 0.1C charge and discharge
Head circulation coulombic efficiency can reach 99.8% or more, with LiCoO2Anode, 1mol/L LiPF4With 1mol/L LiTFSI (solvent
EC:DEC:DMC volume ratio=1:1:1) electrolyte assembling full battery in LiCoO2Positive electrode specific capacity and cycle performance of battery
It significantly improves.
Detailed description of the invention
Fig. 1 is the electroplanting device schematic diagram for preparing passivation of lithium powder；
Fig. 2 is the scanning electron microscope diagram of passivation of lithium powder prepared by embodiment 1；
Fig. 3 is the scanning electron microscope diagram of passivation of lithium powder prepared by embodiment 2；
Fig. 4 is the scanning electron microscope diagram of passivation of lithium powder prepared by embodiment 3；
Fig. 5 is the transmission electron microscope bright field image figure of passivation of lithium powder prepared by embodiment 1；
Fig. 6 is the corresponding dark field image figure of lithium metal diffraction spot of passivation of lithium powder prepared by embodiment 1；
Fig. 7 is that passivation of lithium powder prepared by embodiment 2 does not carry out prelithiation as graphite cathode made from prelithiation agent and
The half-cell head cycle charge-discharge curve graph of graphite cathode；
Fig. 8 is that passivation of lithium powder prepared by embodiment 2 does not carry out prelithiation as silicon-carbon cathode made from prelithiation agent and
The half-cell head cycle charge-discharge curve graph of silicon-carbon cathode；
Fig. 9 is that passivation of lithium powder prepared by embodiment 2 does not carry out prelithiation as graphite cathode made from prelithiation agent and
Graphite cathode and LiCoO2The full battery head cycle charge-discharge curve graph of anode assembling；
Figure 10 is that passivation of lithium powder prepared by embodiment 2 does not carry out prelithiation as silicon-carbon cathode made from prelithiation agent and
Silicon-carbon cathode and LiCoO2The full battery head cycle charge-discharge curve graph of anode assembling；
Figure 11 is the initial digital photograph (a) of the ultra-fine passivation of lithium powder being supported on copper sheet and place prepared by embodiment 1
Digital photograph (b) in the air that humidity is 20% after 30 days.
Specific embodiment
The present invention provides a kind of preparation methods of passivation of lithium powder, comprising the following steps: using lithium salts as electrolyte, with lithium piece
For anode, using inert metal as cathode, it is electroplated under the conditions of existing for the organic solvent and fluorochemical, obtains passivation of lithium
Powder.
In the present invention, the preparation of the passivation of lithium powder carries out preferably in electroplanting device, the electroplanting device such as Fig. 1 institute
Show, using metal lithium sheet as anode, using inert metal as cathode.
In the present invention, if without specified otherwise, all raw material components are commercially available quotient well known to those skilled in the art
Product.
In the present invention, the lithium salts preferably includes LiPF6、LiAsF6, one or more of LiTFSI and LiFSI.In
In the present invention, the fluorochemical preferably includes fluorinated ethylene carbonate and/or ammonium fluoride.In the present invention, described organic
Solvent preferably includes one or more of ether organic solvent or carbonate based organic solvent.In the present invention, the ethers
Organic solvent preferably includes tetrahydrofuran (THF), 1,3- dioxolane (DOL), dimethyl-tetrahydrofuran (2Me-THF) and 1,2-
One or more of dimethoxy-ethane (DME).In the present invention, the carbonate based organic solvent preferably includes carbonic acid second
One or more of enester (EC), propene carbonate (PC), dimethyl carbonate (DMC) and diethyl carbonate (DEC).In this hair
In bright, the amount ratio of the lithium salts, fluorochemical and organic solvent is preferably (0.8~1.5) mmol:(0.05~0.3)
Mmol:1mL, more preferably (0.9~1.2) mmol:(0.05~0.2) mmol:1mL, most preferably 1mmol:0.2mmol:
1mL。
In the present invention, the inert metal preferably includes one or more of copper, platinum and titanium.
In the present invention, the current density of the plating is preferably 0.01~2.0mAcm-2, more preferably 0.05mA
cm-2、0.10mA·cm-2、0.15mA·cm-2、0.20mA·cm-2、0.25mA·cm-2、0.50mA·cm-2、0.75mA·cm-2、1.0mA·cm-2、1.25mA·cm-2、1.50mA·cm-2、1.75mA·cm-2Or 2.0mAcm-2.In the present invention, institute
Stating electroplating time is preferably 0.25~8h, more preferably 0.5h, 1h, 2h, 3h, 4h, 5h, 6h, 7h or 8h.
In the present invention, in the electroplating process, anode metal lithium, which loses electronics and becomes lithium ion, to be dissolved into electrolyte,
Lithium ion is deposited in the inert metal surface of cathode by electrochemical reduction in electrolyte simultaneously, obtains passivation of lithium powder film.
After completing the plating, the present invention it is also preferable to include gained passivation of lithium powder film is successively cleaned, ultrasound removing
And drying.
In the present invention, the solvent that the cleaning uses is preferably organic solvent.In the present invention, the organic solvent
Type is preferably identical as the organic solvent type that above-mentioned plating uses, and details are not described herein.In the present invention, time of the cleaning
Number preferably 2~3 times.In the present invention, the cleaning can remove unreacted lithium salts.
In the present invention, the ultrasound removing carries out preferably in atent solvent.In the present invention, the atent solvent is excellent
Choosing includes cyclic ether 1,3- dioxolanes (DOL), N-Methyl pyrrolidone (NMP), tetrahydrofuran (THF), dimethyl carbonate
(DMC) and one or more of diethyl carbonate (DEC), more preferably 1,3-dioxolane (DOL), N-Methyl pyrrolidone
(NMP), tetrahydrofuran (THF), dimethyl carbonate (DMC) or diethyl carbonate (DEC).Power of the present invention for the ultrasound
It is not particularly limited, using ultrasonic power well known in the art；The time of the ultrasound is preferably 10~30min, more excellent
It is selected as 10min, 15min, 20min, 25min or 30min；The temperature of the ultrasound is preferably room temperature.In the present invention, described super
In sound stripping process, the passivation of lithium powder film is stripped, and obtains the passivation of lithium slurry that passivation of lithium powder and atent solvent are formed
Material.
In the present invention, the mode of the drying is preferably that the glove box of argon gas protection or battery are carried out in stove room；Institute
Stating dry temperature is preferably 20~40 DEG C, more preferably 20 DEG C, 25 DEG C, 30 DEG C；The time of the drying is preferably 8~for 24 hours,
More preferably 8h or 12h.
Preparation method provided by the invention is easy to operate, does not need high-speed stirred and heating equipment, only need to be at room temperature
Ultra-fine passivation of lithium powder can be prepared, after being supported on the lithium powder of cathode inert metal surface by ultrasound removing, cathode inertia
Sheet metal can also be reused, and economize on resources, and reduce production cost.And it obtains passivation of lithium powder both and can directly be prepared into and is pre-
The slurry that lithiumation uses simplifies prelithiation technique, also can be prepared into dry state passivation of lithium powder, be readily transported.
The present invention provides preparation method described in above-mentioned technical proposal preparation passivation of lithium powder, the passivation of lithium powder be with
The spherical shape of nucleocapsid structure, wherein the core of nucleocapsid structure is formed by metallic lithium powder, and the shell of nucleocapsid structure is by lithium fluoride/oxygen
Change lithium compound to be formed.
In the present invention, the passivation of lithium powder is preferably dimensioned to be 0.3~4.0 μm, more preferably 0.3~1 μm, more preferably
It is 0.3~0.6 μm；The shell thickness of the passivation of lithium powder is preferably 10~50nm, more preferably 10nm, 15nm, 20nm,
25nm, 30nm, 35nm, 40nm, 45nm or 50nm.
The present invention also provides the passivation of lithium powder of the preparation of preparation method described in above-mentioned technical proposal or above-mentioned technical proposal institutes
Application of the passivation of lithium powder stated in lithium ion battery.In the present invention, the passivation of lithium powder is preferably as graphite cathode or silicon
The prelithiation reagent of Carbon anode.
In the present invention, the passivation of lithium powder does not carry out prelithiation preferably as silicon-carbon cathode made from prelithiation agent and
Graphite cathode or silicon-carbon cathode composition half-cell or full battery.In the present invention, in the composition of the half-cell, prelithiation graphite
Active material in cathode and silicon-carbon cathode: conductive agent acetylene black: binder Kynoar mass ratio is preferably 80:10:10.
In the present invention, the full battery is preferably using EC:DEC:DMC volume ratio=1:1:1 mixed solvent as solvent, LiPF6For lithium
Salt, concentration 1mol/L, the button full battery assembled using the PP/PE/PP three-layer membrane of commercialization.
Below in conjunction with the embodiment in the present invention, the technical solution in the present invention is clearly and completely described.It is aobvious
So, described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.Based on the reality in the present invention
Example is applied, every other embodiment obtained by those of ordinary skill in the art without making creative efforts all belongs to
In the scope of protection of the invention.
Embodiment 1
It is to have with EC:DEC volume ratio=1:1 mixed solvent in glove box using electroplanting device as shown in Figure 1
Solvent, with LiPF6For electrolyte, copper sheet is cathode, and lithium piece is anode, and FEC is additive, is 0.1mA in current density
cm-2Under conditions of 3h is electroplated, obtain the passivation of lithium powder film for being carried on copper sheet；Wherein, LiPF6, FEC and organic solvent amount ratio
For 1mol:0.1mol:1L；
The copper sheet of the load passivation of lithium powder film is transferred in DOL solvent, ultrasound removing 20min obtains passivation of lithium powder
Passivation of lithium slurry material is placed in evaporation of solvent DOL in the glove box or battery stove room of argon gas protection, obtains passivation of lithium by slurry
Powder.
The scanning electron microscope diagram of gained passivation of lithium powder is as shown in Fig. 2, transmission electron microscope bright field image figure such as Fig. 3 institute
Show, the corresponding dark field image figure of lithium metal diffraction spot is as shown in Figure 4.By Fig. 2~4 it is found that the passivation of lithium powder of preparation is lithium metal
Core-lithium fluoride/lithia shell composition nucleocapsid structure spheric granules, the size of spheric granules is about 1.0 μm, and shell thickness is about
For 20nm.
Embodiment 2
In glove box, using EC:DEC:DMC volume ratio=1:1:1 mixed solvent as organic solvent, LiPF6For electrolysis
Matter, copper sheet are cathode, and lithium piece is anode, and FEC is additive, are 0.05mAcm in current density-2Under conditions of 1h is electroplated, obtain
To the passivation of lithium powder film for being carried on copper sheet；Wherein, LiPF6, FEC and organic solvent amount ratio be 1mol:0.05mol:1L；
The copper sheet of gained load passivation of lithium powder film is transferred in DOL solvent, ultrasound removing 10min obtains passivation of lithium slurry
Passivation of lithium slurry material is placed in evaporation of solvent DOL in the glove box of argon gas protection, obtains passivation of lithium powder by material.
It is the nucleocapsid structure of shell that the structure of obtained passivation of lithium powder, which is by core, lithium fluoride/lithium oxide composite of lithium metal,
Spheric granules；The scanning electron microscope diagram of gained passivation of lithium powder is as shown in figure 5, as shown in Figure 5, the particle ruler of passivation of lithium powder
Very little is 300~600nm, and shell thickness is about 10nm.
Embodiment 3
In glove box, using EC:DEC:THF volume ratio=1:1:1 mixed solvent as organic solvent, LiTFSI is electrolysis
Matter, platinized platinum are cathode, and lithium piece is anode, and FEC is additive, are 0.2mAcm in current density-2Under conditions of 8h is electroplated, obtain
To the passivation of lithium powder film for being carried on platinized platinum；Wherein, the amount ratio of LiTFSI, FEC and organic solvent is 1mol:0.05mol:1L；
The platinized platinum of gained load passivation of lithium powder film is transferred in DOL solvent, ultrasound removing 30min obtains passivation of lithium slurry
Passivation of lithium slurry material is placed in evaporation of solvent DOL in the glove box of argon gas protection, obtains passivation of lithium powder by material.
It is the nucleocapsid structure of shell that the structure of obtained passivation of lithium powder, which is by core, lithium fluoride/lithium oxide composite of lithium metal,
Spheric granules；The scanning electron microscope diagram of gained passivation of lithium powder is as shown in fig. 6, it will be appreciated from fig. 6 that the particle ruler of passivation of lithium powder
Very little about 3.0 μm, shell thickness is about 40nm.
Embodiment 4
In the stove room of battery assembly, using PC:DOL:THF volume ratio=1:1:1 mixed solvent as organic solvent,
LiFSI is electrolyte, and platinized platinum is cathode, and lithium piece is anode, and FEC is additive, is 2.0mAcm in current density-2Condition
Lower plating 6h obtains the passivation of lithium powder film for being carried on platinized platinum；Wherein, the amount ratio of LiFSI, FEC and organic solvent is 1mol:
0.2mol:1L；
The platinized platinum of gained load passivation of lithium powder film is transferred in DOL solvent, ultrasound removing 30min obtains passivation of lithium slurry
Passivation of lithium slurry material is placed in evaporation of solvent DOL in the glove box of argon gas protection, obtains passivation of lithium powder by material.
It is the nucleocapsid structure of shell that the structure of obtained passivation of lithium powder, which is by core, lithium fluoride/lithium oxide composite of lithium metal,
Spheric granules, the particle size of passivation of lithium powder is about 4.0 μm, and shell thickness is about 50nm.
Embodiment 5
In the stove room of battery assembly, using DEC:DOL volume ratio=1:1 mixed solvent as organic solvent, LiTFSI is
Electrolyte, titanium sheet are cathode, and lithium piece is anode, and ammonium fluoride is additive, are 1.0mAcm in current density-2Under conditions of electricity
4h is plated, the passivation of lithium powder film for being carried on platinized platinum is obtained；Wherein, the amount ratio of LiTFSI, FEC and organic solvent is 1mol:
0.2mol:1L；
The titanium sheet of gained load passivation of lithium powder film is transferred in DOL solvent, ultrasound removing 25min obtains passivation of lithium slurry
Material, is placed in evaporation of solvent DOL in battery stove room for passivation of lithium slurry material, obtains passivation of lithium powder.
It is the nucleocapsid structure of shell that the structure of obtained passivation of lithium powder, which is by core, lithium fluoride/lithium oxide composite of lithium metal,
Spheric granules, the particle size of passivation of lithium powder is about 2.0 μm, and shell thickness is about 35nm.
Embodiment 6
In the stove room of battery assembly, using DEC:DOL volume ratio=1:1 mixed solvent as organic solvent, LiAsF6For
Electrolyte, titanium sheet are cathode, and lithium piece is anode, and ammonium fluoride is additive, are 1.0mAcm in current density-2Under conditions of electricity
4h is plated, the passivation of lithium powder film for being carried on platinized platinum is obtained；Wherein, the amount ratio of LiTFSI, FEC and organic solvent is 1mol:
0.2mol:1L；
The titanium sheet of gained load passivation of lithium powder film is transferred in DOL solvent, ultrasound removing 20min obtains passivation of lithium slurry
Passivation of lithium slurry material is placed in evaporation of solvent DOL in the glove box of argon gas protection, obtains passivation of lithium powder by material.
It is the nucleocapsid structure of shell that the structure of obtained passivation of lithium powder, which is by core, lithium fluoride/lithium oxide composite of lithium metal,
Spheric granules, the particle size of passivation of lithium powder is about 2.0 μm, and shell thickness is about 35nm.
Test case 1
Fig. 7 is that passivation of lithium powder prepared by embodiment 2 does not carry out prelithiation as graphite cathode made from prelithiation agent and
The half-cell head cycle charge-discharge curve of graphite cathode, Fig. 8 are the passivation of lithium powder of the preparation of embodiment 2 as made from prelithiation agent
Silicon-carbon cathode and do not carry out prelithiation silicon-carbon cathode half-cell head cycle charge-discharge curve；Wherein, prelithiation graphite cathode
In silicon-carbon cathode, active material: conductive agent acetylene black: binder Kynoar ratio is 80:10:10, is filled using 0.1C
Electric discharge.By Fig. 7~8 it is found that graphite cathode and silicon-carbon cathode half-cell using passivation of lithium powder prelithiation prepared by the present invention are first
Circulation coulombic efficiency reaches 99.8% or more, and cycle performance is excellent.
Fig. 9 is that passivation of lithium powder prepared by embodiment 2 does not carry out prelithiation as graphite cathode made from prelithiation agent and
Graphite cathode and LiCoO2The full battery head cycle charge-discharge curve of anode assembling, Figure 10 are passivation of lithium powder prepared by embodiment 2
The silicon-carbon cathode and LiCoO of prelithiation are not carried out as silicon-carbon cathode made from prelithiation agent and2The full battery of anode assembling is first
Cycle charge-discharge curve；Wherein, full battery is using the mixed solvent of EC:DEC:DMC=1:1:1 as solvent, LiPF6It is dense for lithium salts
Degree is 1mol/L, the button full battery assembled using the PP/PE/PP three-layer membrane of commercialization, using 0.1C charge and discharge.By Fig. 9
~10 it is found that use the graphite cathode and silicon-carbon cathode half-cell head cycling pool of the ultra-fine passivation of lithium powder prelithiation of the invention obtained
Human relations efficiency reaches 99.8% or more；Using LiCoO in the full battery of prelithiation graphite cathode2The specific capacity of anode is 150mA
h·g-1, and use LiCoO in the full battery of non-prelithiation graphite cathode2The specific capacity 132mAhg of anode-1；Using pre- lithium
LiCoO in the full battery of SiClx Carbon anode2The specific capacity of anode is 162mAhg-1, using the complete of non-prelithiation silicon-carbon cathode
LiCoO in battery2The specific capacity of anode is 122mAhg-1.It can be seen that the graphite cathode and silicon-carbon using prelithiation are negative
The full battery of pole assembling, positive specific capacity are effectively promoted.
Test case 2
The initial digital photograph of the passivation of lithium powder being supported on copper sheet prepared by the embodiment of the present invention 1 as shown in a in Figure 11,
The passivation of lithium powder of preparation is placed on to digital photograph b institute such as in Figure 11 of passivation of lithium powder after humidity is 30 days in 20% air
Show.As shown in Figure 11, passivation of lithium powder prepared by the present invention is placed in the air that humidity is 20% and is still stabilized after 30 days,
Structure and ingredient stability are excellent.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of preparation method of passivation of lithium powder, which comprises the following steps: using lithium salts as electrolyte, be with lithium piece
Anode is electroplated under the conditions of existing for the organic solvent and fluorochemical using inert metal as cathode, obtains passivation of lithium
Powder.
2. preparation method according to claim 1, which is characterized in that the lithium salts includes LiPF6、LiAsF6, LiTFSI and
One or more of LiFSI.
3. preparation method according to claim 1, which is characterized in that the fluorochemical includes fluorinated ethylene carbonate
And/or ammonium fluoride；
The organic solvent includes ether organic solvent or carbonate based organic solvent.
4. described in any item preparation methods according to claim 1~3, which is characterized in that the lithium salts, fluorochemical and have
The amount ratio of solvent is (0.8~1.5) mmol:(0.05~0.3) mmol:1mL.
5. preparation method according to claim 1, which is characterized in that the current density of the plating be 0.01~
2.0mA·cm-2, electroplating time is 0.25~8h.
6. preparation method according to claim 1, which is characterized in that further include being passivated gained after the completion of the plating
Lithium powder film is successively cleaned, ultrasound is removed and dry.
7. preparation method according to claim 6, which is characterized in that the ultrasound removing carries out in atent solvent；Institute
Stating atent solvent includes cyclic ether 1,3- dioxolanes, N-Methyl pyrrolidone, tetrahydrofuran, dimethyl carbonate or carbonic acid diethyl
Ester；The time of the ultrasound removing is 10~30min.
8. the passivation of lithium powder of any one of claim 1~7 preparation method preparation, which is characterized in that the passivation of lithium powder be with
The spherical shape of nucleocapsid structure, wherein the core of nucleocapsid structure is formed by metallic lithium powder, and the shell of nucleocapsid structure is by lithium fluoride/oxygen
Change lithium compound to be formed.
9. passivation of lithium powder according to claim 8, which is characterized in that the size of the passivation of lithium powder is 0.3~4.0 μm,
The shell thickness of the passivation of lithium powder is 10~50nm.
10. the passivation of lithium powder or benefit of the preparation method preparation of any one of claim 1~7 require 8~9 described in any item blunt
Change application of the lithium powder in lithium ion battery.
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