CN110212166A - A method of double shielding interface is constructed on lithium an- ode surface - Google Patents
A method of double shielding interface is constructed on lithium an- ode surface Download PDFInfo
- Publication number
- CN110212166A CN110212166A CN201910503536.8A CN201910503536A CN110212166A CN 110212166 A CN110212166 A CN 110212166A CN 201910503536 A CN201910503536 A CN 201910503536A CN 110212166 A CN110212166 A CN 110212166A
- Authority
- CN
- China
- Prior art keywords
- lithium
- ode
- double shielding
- shielding interface
- treatment fluid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- 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
- H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
-
- 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 a kind of methods at lithium an- ode surface building double shielding interface, it forms condensed phosphate the following steps are included: polyphosphoric acids and polyalcohol are carried out esterification by (a)；(b) condensed phosphate is added in organic solvent and is configured to esters treatment fluid；(c) lithium metal piece is immersed in the esters treatment fluid and performs etching reaction.Reaction is performed etching by immersing active lithium metal piece in the specific ester treatment fluid containing certain mass content; organic/inorganic bi-layer interface protective layer can be formed by etching in situ in metal surface in this way; the sheet metal storage stable in the air that makes that treated in this way, can greatly improve its cycle performance and security performance when being used for lithium metal battery.
Description
Technical field
The invention belongs to lithium metal battery fields, are related to a kind of construction method of lithium an- ode protective layer, and in particular to
A method of double shielding interface is constructed on lithium an- ode surface.
Background technique
In recent years, this is directly facilitated as electric car, power grid energy storage and portable electronic product etc. must continue to develop
The research of high energy density cells.Lithium metal has highest specific capacity (3860mAh g-1) and minimum oxidation-reduction potential
(- 3.04 V vs SHE), thus be considered as the potential candidate for substituting existing commercial li-ion cell negative electrode material.However,
Lithium metal with high reaction activity can be spontaneous with organic electrolysis qualitative response, to form unstable solid electrolyte interface
Layer (SEI).And plating/the stripping process constantly occurred on lithium metal surface can cause the great variety of lithium metal volume itself,
And destroyed with the structure of SEI film, fragmentation, and form crackle on lithium metal surface, this can cause lithium concentration in electrolyte
Uneven distribution, cracks lithium concentration is bigger than normal, causes dendritic heterogeneity lithium to deposit, and then cause Li dendrite
Growth.Li dendrite is easy to pierce through diaphragm during the growth process, causes internal short-circuit and causes safety problem.In addition, SEI film
Repeatability cracking and the growth of Li dendrite lithium simple substance can be exposed in organic bath, and constantly with electrolysis qualitative response
Form new SEI layer.This leads to the rapidly depleting and serious lithium corrosion process of electrolyte, and further influences battery
Coulombic efficiency and service life.Therefore, artificial modification SEI layers are still the key for realizing high-performance lithium metal negative electrode.
In recent years, there has been proposed the strategies of many stable lithium anodes.By the composition to electrolyte, such as add
Agent, high concentration electrolyte and solid electrolyte etc. optimize, and the stability for the SEI layer being formed in situ can be improved；But this
The mechanical property of SEI layers of kind is poor, is still difficult to avoid that the various problems of the foregoing description, thus cyclical stability is poor；By having
The ex situ coating of machine polymer, inorganic ceramic and its hybrid composition, has the stronger machine for SEI layers in situ
Tool intensity.It thus introduces this ex situ coating on lithium metal surface and can significantly improve the brittleness that SEI in situ is faced and ask
Topic.However, the problems such as ionic conductivity is low, the mechanical strength of polymer is insufficient, the interfacial contact of ceramics is bad is still lithium gold
Belong to the inevitable problem of cathode in actual application.Therefore, construct it is a kind of it is structurally reasonable, can provide simultaneously quickly
The protective layer in lithium ion transport channel, high mechanical modulus and good morphological consistency has a very important significance.
Summary of the invention
It is provided the invention aims to overcome the deficiencies in the prior art a kind of double-deck in the building of lithium an- ode surface
The method for protecting interface.
In order to achieve the above objectives, the technical solution adopted by the present invention is that: it is a kind of to construct double-deck protect on lithium an- ode surface
Protect interface method, it the following steps are included:
(a) polyphosphoric acids and polyalcohol are subjected to esterification and form condensed phosphate；
(b) condensed phosphate is added in organic solvent and is configured to esters treatment fluid；
(c) lithium metal piece is immersed in the esters treatment fluid and performs etching reaction.
Optimally, it further include:
(d) step (c) treated the lithium metal piece is cleaned with anhydrous solvent, removes the residual on its surface
Liquid is placed under vacuum condition and is dried.
Optimally, in step (a), the polyalcohol is selected from ethylene glycol, propylene glycol, butanediol, diethylene glycol (DEG), new penta 2
Alcohol, glycerine, trimethylolethane, trimethylolpropane, xylitol, D-sorbite, sucrose, neopentyl glycol, pentaerythrite,
The mixture of one of polyoxypropyleneglycol and polytetrahydrofuran diol or a variety of compositions.
Optimally, in step (a), the molar ratio of the polyphosphoric acids and polyalcohol is 1:1~6.
Further, in step (a), the reaction temperature of the esterification is 60~200 DEG C, reaction time 30min
~24 h.
Optimally, in step (b), the organic solvent is selected from hexamethylene, tetrahydrofuran, N-Methyl pyrrolidone, third
The mixture of one of ketone and dimethylformamide or a variety of compositions.
Further, in step (b), the mass concentration of condensed phosphate is 0.1%~10% in the esters treatment fluid.
Optimally, in step (c), the time of the etching reaction is 30min~8h.
Due to the above technical solutions, the present invention has the following advantages over the prior art: the present invention is in lithium metal
The method that negative terminal surface constructs double shielding interface, by the way that active lithium metal piece is immersed the spy containing certain mass content
Determine to perform etching reaction in esters treatment fluid, organic/inorganic bi-layer circle can be formed by etching in situ in metal surface in this way
Face protective layer, so that sheet metal storage stable in the air that treated can be mentioned substantially when being used for lithium metal battery
Its high cycle performance and security performance.
Detailed description of the invention
Fig. 1 is the scanning electron microscope (SEM) photograph that two layer interface made from embodiment 1 protects lithium an- ode；
Fig. 2 is that two layer interface made from embodiment 1 protects lithium an- ode scanning electron microscope sectional view；
Fig. 3 is that two layer interface made from embodiment 1 protects lithium an- ode to assemble lithium Symmetrical cells cyclic polarization curve；
Fig. 4 is that two layer interface made from embodiment 1 protects lithium an- ode to be assembled into Li/LiFePO4Charge and discharge after battery
Electric curve；
Fig. 5 is the Li/LiFePO that two layer interface made from embodiment 1 protects lithium an- ode to be assembled into4Battery and comparison
The circulation comparison diagram of example battery；
Fig. 6 is that two layer interface made from embodiment 1 protects lithium an- ode and the storage of the common lithium an- ode of comparative example
The Li/LiFePO assembled respectively after 30min in air4The circulation comparison diagram of battery；
Fig. 7 is that two layer interface made from embodiment 1 protects lithium an- ode and the common lithium piece of comparative example to be assembled into respectively
Solid-state Li/LiFePO4The circulation comparison diagram of battery；
Fig. 8 is that two layer interface made from embodiment 1 protects lithium an- ode to be assembled into Li/S battery and comparative example battery
Recycle comparison diagram；
Fig. 9 is the Li/LiCoO that two layer interface made from embodiment 1 protects lithium an- ode to be assembled into2Battery and comparative example
The circulation comparison diagram of battery；
Two layer interface made from Figure 10 embodiment 1 protects lithium an- ode and the common lithium piece of comparative example in cycle charge-discharge
Scanning electron microscope comparison diagram after 100 circles.
Specific embodiment
The present invention lithium an- ode surface building double shielding interface method, it the following steps are included: (a) by poly
Phosphoric acid and polyalcohol carry out esterification and form condensed phosphate；(b) condensed phosphate is added in organic solvent and is prepared
At esters treatment fluid；(c) lithium metal piece is immersed in the esters treatment fluid and performs etching reaction.By will be active
Lithium metal piece, which immerses in the specific ester treatment fluid containing certain mass content, performs etching reaction, in this way can be in metal watch
Face forms organic/inorganic bi-layer interface protective layer by etching in situ, so that treated, and sheet metal is stable in the air
Storage, can greatly improve its cycle performance and security performance when being used for lithium metal battery；Metal lithium sheet after treatment
Can make lithium two layer interface protection in uniformly deposit, effectively inhibit Li dendrite growth, and alleviate lithium metal plating/
Volume change in stripping process.
The above method can also include step (d): step (c) treated the lithium metal piece is carried out with anhydrous solvent
Cleaning, removes the Liquid Residue on its surface, is placed under vacuum condition and is dried.In step (a), the polyalcohol is selected from second
Glycol, propylene glycol, butanediol, diethylene glycol (DEG), neopentyl glycol, glycerine, trimethylolethane, trimethylolpropane, xylitol,
One of D-sorbite, sucrose, neopentyl glycol, pentaerythrite, polyoxypropyleneglycol and polytetrahydrofuran diol are a variety of
The mixture of composition；Optimal is pentaerythrite.In step (a), the molar ratio of the polyphosphoric acids and polyalcohol is 1:1~6.
In step (a), the reaction temperature of the esterification is 60~200 DEG C of (preferably 100~150 DEG C), reaction time 30min
~24 h (preferably 6~12h).In step (b), the organic solvent is selected from hexamethylene, tetrahydrofuran, N- crassitude
The mixture of one of ketone, acetone and dimethylformamide or a variety of compositions；Condensed phosphate in the esters treatment fluid
Mass concentration is 0.1%~10%.In step (c), the time of the etching reaction is 30min~8h.
Below in conjunction with example, invention is further explained.
Embodiment 1
The present embodiment provides a kind of methods at lithium an- ode surface building double shielding interface, it includes following step
It is rapid:
(a) it synthesizes organophosphorus ester precursor: 4.2g polyphosphoric acids being added in single-necked flask, and is warming up to 120 DEG C, with
1g pentaerythrite is added afterwards, stirs evenly, reacts 6h under the conditions of 100 DEG C of temperature；
(b) it configures esters treatment fluid: in the glove box full of argon gas, 80mg organophosphorus ester being added to 20mL tetra-
In hydrogen furans, keeps its evenly dispersed and form esters treatment fluid；
(c) 1 metal lithium sheet is taken, the passivation layer on surface is fallen with fine, soft fur brushing, lithium piece is then completely immersed in esters processing
In liquid, 1h is impregnated at room temperature；
(d) it after taking out lithium piece, is cleaned multiple times (3~5 times) with hexamethylene, and draws remaining esters with dust-free paper
Treatment fluid and hexamethylene (more importantly removing condensed phosphate), then be placed under vacuum condition and dry.
Embodiment 2
The present embodiment provides a kind of method at lithium an- ode surface building double shielding interface, in it and embodiment 1
Operating procedure it is almost the same, unlike: in step (a), the synthesis temperature of organophosphorus ester precursor is 200 DEG C.
Embodiment 3
The present embodiment provides a kind of method at lithium an- ode surface building double shielding interface, in it and embodiment 1
Operating procedure it is almost the same, unlike: in step (a), the generated time of organophosphorus ester precursor is 12h.
Embodiment 4
The present embodiment provides a kind of method at lithium an- ode surface building double shielding interface, in it and embodiment 1
Operating procedure it is almost the same, unlike: in step (b), the content for the organophosphorus ester being added in tetrahydrofuran solvent
For 40mg.
Embodiment 5
The present embodiment provides a kind of method at lithium an- ode surface building double shielding interface, in it and embodiment 1
Operating procedure it is almost the same, unlike: in step (b), the mass concentration of condensed phosphate is in esters treatment fluid
0.1%.
Embodiment 6
The present embodiment provides a kind of method at lithium an- ode surface building double shielding interface, in it and embodiment 1
Operating procedure it is almost the same, unlike: in step (b), the mass concentration of condensed phosphate is in esters treatment fluid
10%.
Embodiment 7
The present embodiment provides a kind of method at lithium an- ode surface building double shielding interface, in it and embodiment 1
Operating procedure it is almost the same, unlike: in step (c), lithium piece impregnates the reaction time in esters treatment fluid for 30min.
Embodiment 8
The present embodiment provides a kind of method at lithium an- ode surface building double shielding interface, in it and embodiment 1
Operating procedure it is almost the same, unlike: in step (c), lithium piece impregnates the reaction time in esters treatment fluid for 4h.
Embodiment 9
The present embodiment provides a kind of method at lithium an- ode surface building double shielding interface, in it and embodiment 1
Operating procedure it is almost the same, unlike: in step (c), lithium piece impregnates the reaction time in esters treatment fluid for 8h.
Embodiment 10
The present embodiment provides a kind of method at lithium an- ode surface building double shielding interface, in it and embodiment 1
Operating procedure it is almost the same, unlike: in step (a), the molar ratio of polyphosphoric acids and pentaerythrite is 1:1.
Embodiment 11
The present embodiment provides a kind of method at lithium an- ode surface building double shielding interface, in it and embodiment 1
Operating procedure it is almost the same, unlike: in step (a), the molar ratio of polyphosphoric acids and pentaerythrite is 1:6.
Embodiment 12
The present embodiment provides a kind of method at lithium an- ode surface building double shielding interface, in it and embodiment 1
Operating procedure it is almost the same, unlike: in step (a), the polyalcohol being added in polyphosphoric acids is that propylene glycol is (other
The glycol such as ethylene glycol, butanediol, diethylene glycol (DEG), neopentyl glycol, neopentyl glycol, polyoxypropyleneglycol and polytetrahydrofuran diol
It is almost the same with the using effect of propylene glycol).
Embodiment 13
The present embodiment provides a kind of method at lithium an- ode surface building double shielding interface, in it and embodiment 1
Operating procedure it is almost the same, unlike: in step (a), be added polyphosphoric acids in polyalcohol be trimethylolethane
(using effect of the triols such as other glycerine, trimethylolpropane and trimethylolethane is almost the same).
Embodiment 14
The present embodiment provides a kind of method at lithium an- ode surface building double shielding interface, in it and embodiment 1
Operating procedure it is almost the same, unlike: in step (a), be added polyphosphoric acids in be xylitol (D-sorbite and sugarcane
The using effect of sugar and xylitol is almost the same).
Comparative example 1
This example provides a kind of method at lithium an- ode surface building double shielding interface, the behaviour in it and embodiment 1
It is almost the same to make step, unlike: in step (a), the molar ratio of polyphosphoric acids and pentaerythrite is 1:8.
Comparative example 2
This example provides a kind of method at lithium an- ode surface building double shielding interface, the behaviour in it and embodiment 1
It is almost the same to make step, unlike: in step (b), the mass concentration of condensed phosphate is excessively high in esters treatment fluid, is
15%.
Comparative example 3
This example provides a kind of method at lithium an- ode surface building double shielding interface, the behaviour in it and embodiment 1
It is almost the same to make step, unlike: step (a) is not carried out, and directly replaces condensed phosphate using polyphosphoric acids.
Experimental example
This example provides the method for assembling different batteries as cathode using lithium piece obtained in above-mentioned each example, specific as follows:
(1) by LiFePO4Powder: acetylene black: PVDF is mixed in the ratio of 8:1:1, and suitable N- crassitude is added
Ketone (NMP) be used as dispersing agent, in the agate mortar by mixture grind uniformly, then slurry coating with aluminum foil current collector on,
It is (in single pole piece active to be finally cut into pole piece that diameter is 13mm with slicer by the dry 12h in 60 DEG C of vacuum oven
The quality of substance is averagely about 4mg/cm2)；By the metal lithium sheet handled in embodiment 1~14, comparative example 1-3 and untreated
Metal lithium sheet (comparison) be used as Li/LiFePO4The cathode of battery, electrolyte system used are 1M lithium hexafluoro phosphate (LiPF6)
It is dissolved in ethylene carbonate (EC)/diethyl carbonate (DEC) mixed solution that volume ratio is 1:1, is assembled into Li/LiFePO4Battery
Carry out electrochemical property test.The dry lithium piece completed is exposed in air after 30min simultaneously and is assembled again by same procedure
At Li/LiFePO4Battery carries out battery performance test (performance test data is shown in Table 1).
(2) by LiFePO4Powder: acetylene black: PVDF is mixed in the ratio of 8:1:1, and suitable N- crassitude is added
Ketone (NMP) be used as dispersing agent, in the agate mortar by mixture grind uniformly, then slurry coating with aluminum foil current collector on,
It is (in single pole piece active to be finally cut into pole piece that diameter is 13mm with slicer by the dry 12h in 60 DEG C of vacuum oven
The quality of substance is averagely about 4mg/cm2), it regard the lithium piece (in embodiment 1) being completely dried after reaction as cathode, dissolution
There is LiPF6PEO as solid electrolyte, dress up Li/LiFePO4Electrochemical property test is carried out after all-solid-state battery.Test
As a result see attached drawing.
(3) by sulphur powder: acetylene black: PVDF is mixed in the ratio of 7:2:1, and suitable N-Methyl pyrrolidone (NMP) is added
As dispersing agent, in the agate mortar by mixture grind uniformly, then slurry coating with aluminum foil current collector on, at 60 DEG C
Dry 12h in vacuum oven is finally cut into pole piece that diameter is 13mm (sulphur active material in single pole piece with slicer
Quality is averagely about 1.2mg/cm2), by the lithium piece (in embodiment 1) being completely dried after reaction as the negative of Li/S battery
Pole, electrolyte system used are 1, the 3- dioxy that 1M bis- (trimethyl fluoride sulfonyl) imine lithium (LiTFSI) is dissolved in that volume ratio is 1:1
Penta ring (DOL) // glycol dimethyl ether (DME) mixed solution is assembled into Li/S battery and carries out electrochemical property test.Test knot
Fruit sees attached drawing.
(4) by LiCoO2Powder: acetylene black: PVDF is mixed in the ratio of 8:1:1, and suitable N- crassitude is added
Ketone (NMP) be used as dispersing agent, in the agate mortar by mixture grind uniformly, then slurry coating with aluminum foil current collector on,
It is (in single pole piece active to be finally cut into pole piece that diameter is 13mm with slicer by the dry 12h in 60 DEG C of vacuum oven
The quality of substance is averagely about 4mg/cm2), it regard the lithium piece (in embodiment 1) being completely dried after reaction as Li/LiCoO2
The cathode of battery, electrolyte system used are 1M LiPF6It is dissolved in the EC/DEC mixed solution that volume ratio is 1:1, is assembled into Li/
LiCoO2Battery carries out electrochemical property test.Test result is shown in attached drawing.
Fig. 1 and Fig. 2 is the protection lithium an- ode scanning electron microscope (SEM) photograph of two layer interface made from embodiment 1 and Electronic Speculum section respectively
Figure, it can be seen that the condensed phosphate generated by the esterification between polyphosphoric acids and pentaerythrite is dispersed in
In tetrahydrofuran solvent, metal lithium sheet shows the pattern of uniform ground in the rear surface impregnated, and generate simultaneously it is organic/
Inorganic bi-layer boundary layer, to enable Li | Li battery lithium ion in cyclic process uniformly sinks on lithium an- ode surface
Product, effectively inhibits the growth of Li dendrite.Fig. 3 is that two layer interface made from embodiment 1 protects lithium an- ode assembling lithium symmetrical
The cyclic polarization curve comparison of battery and the lithium Symmetrical cells of common lithium piece assembling；From figure 3, it can be seen that two layer interface is protected
Shield lithium an- ode can keep the polarization potential of very little for a long time.Lithium an- ode in embodiment 1 dresses up Li/
LiFePO4Afterwards, the charging and discharging curve measured is as shown in Figure 4.Fig. 5 is the protection lithium of two layer interface made from embodiment 1 and comparative example
Metal negative electrode is assembled into Li/LiFePO4The circulation comparison diagram of battery, it can be seen that lithium piece of the invention can maintain Li/
LiFePO4The circulation steady in a long-term of battery.Two layer interface protection lithium an- ode of the invention stable in the air can exist,
Fig. 6 is to protect the common lithium piece of lithium an- ode and comparative example to be exposed in air after 30min the two layer interface of embodiment 1
Ressemble Li/LiFePO4The comparison for the circulating battery that battery measures, it can be seen that common lithium piece is led due to being fully oxidized
Cause cell performance decay violent, and two layer interface protects lithium an- ode not influence its electrification after 30min in being exposed to air
Performance is learned, excellent cyclical stability still can be maintained.Fig. 7 is the protection lithium an- ode of two layer interface made from embodiment 1
The solid-state Li/ LiFePO being assembled into respectively with the common lithium piece of comparative example4The circulation comparison diagram of battery, it can be seen that of the invention
Two layer interface protects lithium an- ode also to have positive effect on maintaining solid state battery cyclical stability.Fig. 8 and Fig. 9 is not real
Apply Li/S and Li/LiCoO that the protection lithium an- ode of two layer interface made from example 1 is assembled into2Battery is electric with corresponding comparative example
The circulation comparison diagram in pond illustrates that two layer interface protection lithium an- ode of the invention can also keep being based on sulphur and LiCoO2Just
The cyclical stability of the battery of pole material.Still can to prove to be formed by two layer interface structure after battery long process
It is enough stabilized, the battery in embodiment 1 is disassembled after circulation 100 times, with the pattern on SEM observation lithium metal surface.
Likewise, the battery in comparative example also disassemble and analyze its surface topography after circulation 100 times.Figure 10 is two
The comparison of person's pattern, it can be seen that two layer interface protection lithium an- ode of the invention is still able to maintain original after long-term circulation
Flat configuration, surface does not find the formation of Li dendrite yet.And the lithium piece in comparative example has largely in circulation rear surface for a long time
Dendroid lithium is formed.By organic/electrodeless two layer interface layer formed in metallic lithium surface, wherein bottom inorganic layer has height
Young's modulus can effectively inhibit the growth of Li dendrite；Upper organic layer then has excellent viscoplasticity, can alleviate lithium
Volume change of the metal in plating/stripping process.In addition, this organic/inorganic composite protection layer can enable that treated lithium piece
Presence stable in the air.Its cycle performance and security performance can be greatly improved when being used for lithium metal battery.Party's legal system
For simple, raw material is cheap and easy to get, is suitable for large-scale production, have a good application prospect.
Using two layer interface obtained in embodiment 1-14, comparative example 1-3 protection lithium an- ode as Li/LiFePO4Electricity
Pond cathode carries out battery performance test, and the results are shown in table 1, it can be seen that they still maintain higher appearance after 150 circles
Amount has good cycle performance and security performance.
Lithium an- ode is as Li/LiFePO in 1 embodiment 1-14 of table, comparative example 1-34The performance table of battery cathode
The foregoing examples are merely illustrative of the technical concept and features of the invention, its object is to allow person skilled in the art
It cans understand the content of the present invention and implement it accordingly, it is not intended to limit the scope of the present invention.It is all smart according to the present invention
Equivalent change or modification made by refreshing essence, should be covered by the protection scope of the present invention.
Claims (8)
1. it is a kind of lithium an- ode surface building double shielding interface method, which is characterized in that it the following steps are included:
(a) polyphosphoric acids and polyalcohol are subjected to esterification and form condensed phosphate；
(b) condensed phosphate is added in organic solvent and is configured to esters treatment fluid；
(c) lithium metal piece is immersed in the esters treatment fluid and performs etching reaction.
2. according to claim 1 in the method at lithium an- ode surface building double shielding interface, which is characterized in that it is also
Include:
(d) step (c) treated the lithium metal piece is cleaned with anhydrous solvent, removes the Liquid Residue on its surface, sets
It is dried under vacuum condition.
3. according to claim 1 in the method at lithium an- ode surface building double shielding interface, it is characterised in that: step
(a) in, the polyalcohol is selected from ethylene glycol, propylene glycol, butanediol, diethylene glycol (DEG), neopentyl glycol, glycerine, trihydroxy methyl second
Alkane, trimethylolpropane, xylitol, D-sorbite, sucrose, neopentyl glycol, pentaerythrite, polyoxypropyleneglycol and poly- tetrahydro
The mixture of one of furans glycol or a variety of compositions.
4. according to claim 1 in the method at lithium an- ode surface building double shielding interface, it is characterised in that: step
(a) in, the molar ratio of the polyphosphoric acids and polyalcohol is 1:1 ~ 6.
5. the methods for constructing double shielding interface on lithium an- ode surface according to claim 1 or described in 4, it is characterised in that:
In step (a), the reaction temperature of the esterification is 60 ~ 200 DEG C, the reaction time is the h of 30 min ~ 24.
6. according to claim 1 in the method at lithium an- ode surface building double shielding interface, it is characterised in that: step
(b) in, the organic solvent is in hexamethylene, tetrahydrofuran, N-Methyl pyrrolidone, acetone and dimethylformamide
The mixture of one or more compositions.
7. the method according to claim 1 or 6 at lithium an- ode surface building double shielding interface, it is characterised in that:
In step (b), the mass concentration of condensed phosphate is 0.1% ~ 10% in the esters treatment fluid.
8. according to claim 1 in the method at lithium an- ode surface building double shielding interface, it is characterised in that: step
(c) in, the time of the etching reaction is the h of 30 min ~ 8.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910503536.8A CN110212166B (en) | 2019-06-12 | 2019-06-12 | Method for constructing double-layer protection interface on surface of lithium metal negative electrode |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910503536.8A CN110212166B (en) | 2019-06-12 | 2019-06-12 | Method for constructing double-layer protection interface on surface of lithium metal negative electrode |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110212166A true CN110212166A (en) | 2019-09-06 |
| CN110212166B CN110212166B (en) | 2020-07-28 |
Family
ID=67792089
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910503536.8A Active CN110212166B (en) | 2019-06-12 | 2019-06-12 | Method for constructing double-layer protection interface on surface of lithium metal negative electrode |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110212166B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111416102A (en) * | 2020-04-17 | 2020-07-14 | 苏州清陶新能源科技有限公司 | Gel composite negative plate and preparation method and application thereof |
| WO2023169022A1 (en) * | 2022-03-07 | 2023-09-14 | 华中科技大学 | Method for processing and recycling ultrathin lithium foil, and product |
Citations (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1037293A1 (en) * | 1999-03-16 | 2000-09-20 | Sumitomo Chemical Company, Limited | Non-aqueous electrolyte and lithium secondary battery using the same |
| CN1489229A (en) * | 2002-10-12 | 2004-04-14 | ����Sdi��ʽ���� | Lithium method anode of lithium cell |
| CN101640292A (en) * | 2008-08-01 | 2010-02-03 | 三星Sdi株式会社 | Electrolyte for lithium ion secondary battery, lithium ion secondary battery and manufacturing method thereof |
| US20110183203A1 (en) * | 2010-01-27 | 2011-07-28 | Molecular Nanosystems, Inc. | Polymer supported electrodes |
| US20140080006A1 (en) * | 2012-09-19 | 2014-03-20 | Ohara Inc. | All-solid lithium ion secondary battery |
| JP2014127417A (en) * | 2012-12-27 | 2014-07-07 | Nissan Motor Co Ltd | Method for collecting and reusing negative electrode active material of lithium ion battery |
| CN104471780A (en) * | 2012-07-17 | 2015-03-25 | 日本电气株式会社 | Lithium secondary battery |
| CN104617259A (en) * | 2015-01-06 | 2015-05-13 | 中国科学院化学研究所 | Method for protective treatment of lithium cathodes in lithium secondary batteries |
| CN105051944A (en) * | 2013-03-15 | 2015-11-11 | 锡安能量公司 | Protected electrode structures and methods |
| CN105190969A (en) * | 2013-03-15 | 2015-12-23 | 赛昂能源有限公司 | Protective structures for electrodes |
| CN105409047A (en) * | 2013-07-31 | 2016-03-16 | 株式会社Adeka | Lithium secondary battery and electrolyte solution for lithium secondary batteries |
| CN106099041A (en) * | 2016-08-26 | 2016-11-09 | 深圳博磊达新能源科技有限公司 | A kind of lithium titanate composite negative pole pole piece and lithium titanate battery |
| CN106299253A (en) * | 2015-12-29 | 2017-01-04 | 山东精工电子科技有限公司 | A kind of preparation method of lithium ion battery negative electrode |
| CN107819151A (en) * | 2017-10-31 | 2018-03-20 | 江汉大学 | A kind of non-ignitable hybrid solid-state polymer dielectric and its application in solid secondary batteries |
| CN108075106A (en) * | 2017-11-22 | 2018-05-25 | 中国科学院化学研究所 | A kind of adaptive elastic nano decorative layer preparation method of lithium anode |
| CN108461724A (en) * | 2018-03-05 | 2018-08-28 | 苏州大学 | A kind of preparation method of high security metal composite negative pole |
| CN108711609A (en) * | 2018-05-15 | 2018-10-26 | 清陶（昆山）新能源材料研究院有限公司 | A kind of lithium an- ode process of surface treatment and its application |
| CN109494406A (en) * | 2018-11-14 | 2019-03-19 | 中国科学院宁波材料技术与工程研究所 | A kind of lithium metal battery electrolyte and lithium metal battery |
-
2019
- 2019-06-12 CN CN201910503536.8A patent/CN110212166B/en active Active
Patent Citations (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1037293A1 (en) * | 1999-03-16 | 2000-09-20 | Sumitomo Chemical Company, Limited | Non-aqueous electrolyte and lithium secondary battery using the same |
| CN1489229A (en) * | 2002-10-12 | 2004-04-14 | ����Sdi��ʽ���� | Lithium method anode of lithium cell |
| CN101640292A (en) * | 2008-08-01 | 2010-02-03 | 三星Sdi株式会社 | Electrolyte for lithium ion secondary battery, lithium ion secondary battery and manufacturing method thereof |
| US20110183203A1 (en) * | 2010-01-27 | 2011-07-28 | Molecular Nanosystems, Inc. | Polymer supported electrodes |
| CN104471780A (en) * | 2012-07-17 | 2015-03-25 | 日本电气株式会社 | Lithium secondary battery |
| US20140080006A1 (en) * | 2012-09-19 | 2014-03-20 | Ohara Inc. | All-solid lithium ion secondary battery |
| JP2014127417A (en) * | 2012-12-27 | 2014-07-07 | Nissan Motor Co Ltd | Method for collecting and reusing negative electrode active material of lithium ion battery |
| CN105051944A (en) * | 2013-03-15 | 2015-11-11 | 锡安能量公司 | Protected electrode structures and methods |
| CN105190969A (en) * | 2013-03-15 | 2015-12-23 | 赛昂能源有限公司 | Protective structures for electrodes |
| CN105409047A (en) * | 2013-07-31 | 2016-03-16 | 株式会社Adeka | Lithium secondary battery and electrolyte solution for lithium secondary batteries |
| CN104617259A (en) * | 2015-01-06 | 2015-05-13 | 中国科学院化学研究所 | Method for protective treatment of lithium cathodes in lithium secondary batteries |
| CN106299253A (en) * | 2015-12-29 | 2017-01-04 | 山东精工电子科技有限公司 | A kind of preparation method of lithium ion battery negative electrode |
| CN106099041A (en) * | 2016-08-26 | 2016-11-09 | 深圳博磊达新能源科技有限公司 | A kind of lithium titanate composite negative pole pole piece and lithium titanate battery |
| CN107819151A (en) * | 2017-10-31 | 2018-03-20 | 江汉大学 | A kind of non-ignitable hybrid solid-state polymer dielectric and its application in solid secondary batteries |
| CN108075106A (en) * | 2017-11-22 | 2018-05-25 | 中国科学院化学研究所 | A kind of adaptive elastic nano decorative layer preparation method of lithium anode |
| CN108461724A (en) * | 2018-03-05 | 2018-08-28 | 苏州大学 | A kind of preparation method of high security metal composite negative pole |
| CN108711609A (en) * | 2018-05-15 | 2018-10-26 | 清陶（昆山）新能源材料研究院有限公司 | A kind of lithium an- ode process of surface treatment and its application |
| CN109494406A (en) * | 2018-11-14 | 2019-03-19 | 中国科学院宁波材料技术与工程研究所 | A kind of lithium metal battery electrolyte and lithium metal battery |
Non-Patent Citations (1)
| Title |
|---|
| JIE LIU，ET AL.: "Use of tween polymer to enhance the compatibility of the Li electrolyte interface for the high-performance and high-safety quasi-solid-state lithium-sulfur battery", 《NANO LETTERS》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111416102A (en) * | 2020-04-17 | 2020-07-14 | 苏州清陶新能源科技有限公司 | Gel composite negative plate and preparation method and application thereof |
| CN111416102B (en) * | 2020-04-17 | 2022-04-12 | 苏州清陶新能源科技有限公司 | Gel composite negative plate and preparation method and application thereof |
| WO2023169022A1 (en) * | 2022-03-07 | 2023-09-14 | 华中科技大学 | Method for processing and recycling ultrathin lithium foil, and product |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110212166B (en) | 2020-07-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106159200B (en) | A kind of lithium anode and its preparation and application with protective coating | |
| CN113629236B (en) | Composite metal lithium cathode and preparation method and application thereof | |
| CN110534706B (en) | Passivated lithium powder and preparation method and application thereof | |
| CN110010895B (en) | Carbon fiber loaded magnesium oxide particle cross-linked nanosheet array composite material and preparation method and application thereof | |
| CN106848241A (en) | A kind of preparation method of polymer overmold lithium ion battery electrode material | |
| CN112635709B (en) | SEI film forming agent for negative electrode of sodium ion battery, pre-sodium treatment method and sodium ion battery | |
| CN113036153A (en) | Copper-based current collector for inducing preferential transverse deposition of lithium metal negative electrode and preparation method and application thereof | |
| CN109167063A (en) | A kind of lithium anode and its preparation method and application of artificial solid electrolyte interface layer protection | |
| CN110429243A (en) | A kind of preparation method of high specific energy secondary cell lithium anode | |
| CN108321432A (en) | It is a kind of to be used to inhibit carbon nitrogen polymer reference solid state electrolyte of lithium dendrite growth and its preparation method and application | |
| CN108365172A (en) | A kind of lithium an- ode material and its preparation method and application of natural polymers protection | |
| CN106803593A (en) | A kind of complex function conductive coating and preparation method thereof | |
| CN110311093A (en) | Application, Symmetrical cells, full battery and preparation method of the graphene film in lithium metal battery cathode | |
| CN111193031A (en) | Lithium metal battery cathode and modification method thereof | |
| CN108550902A (en) | A kind of all-solid lithium-ion battery and its in-situ preparation method | |
| CN110265626A (en) | Positive pole piece, preparation method thereof and lithium ion secondary battery | |
| CN110212166A (en) | A method of double shielding interface is constructed on lithium an- ode surface | |
| CN110265622A (en) | Positive electrode plate and lithium ion secondary battery | |
| CN109449376B (en) | Composite lithium metal electrode and preparation method thereof | |
| CN112421115B (en) | Lithium metal-based battery with copper selenide in-situ coated foam copper as lithium metal carrier and preparation method thereof | |
| CN109148954A (en) | A kind of electrolysis additive of high-pressure solid ferric phosphate lithium cell and electrolyte containing the additive | |
| CN105098159A (en) | Cathode material, anode, battery and preparation method of cathode material | |
| CN108630864A (en) | A kind of cathode and diaphragm integral structure and preparation method thereof and battery | |
| CN111668492A (en) | Lithium metal negative electrode current collector, preparation method thereof, composite negative electrode and lithium metal secondary battery | |
| CN116706000A (en) | Sustainable flexible protective layer modified lithium metal negative electrode and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20220810 Address after: 215000 F4, building 11, No. 2288, Wuzhong Avenue, Wuzhong Economic Development Zone, Suzhou, Jiangsu Province Patentee after: Suzhou Dega Energy Technology Co.,Ltd. Address before: No. 8, Xiangcheng District Ji Xue Road, Suzhou, Jiangsu Patentee before: SOOCHOW University |
|
| TR01 | Transfer of patent right |