CN109473710A - A kind of solid state lithium battery with low interfacial resistance - Google Patents
A kind of solid state lithium battery with low interfacial resistance Download PDFInfo
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
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Abstract
A kind of solid state lithium battery with low interfacial resistance, belong to can charge and discharge high specific energy technical field of secondary batteries.The solid state battery is made of anode, inorganic solid electrolyte, lithium anode and boundary moisture agent.Boundary moisture agent is respectively present between anode and inorganic solid electrolyte and between lithium anode and inorganic solid electrolyte；The boundary moisture agent contains ether-ether class mixed solvent and lithium salts, and boundary moisture agent forms solid-state interface film after electrochemical in-situ is handled.The boundary moisture agent can significantly reduce the interface resistance inside solid state lithium battery, to enable battery to work normally under room temperature and larger multiplying power, so that the safety of battery be enable to be obviously improved；Compatible a variety of oxidized form inorganic solid electrolytes simultaneously have versatility in a certain range.
Description
Technical field
The present invention relates to a kind of solid state lithium battery with low interfacial resistance, belong to can charge and discharge high specific energy secondary cell skill
Art field.
Background technique
With the fast development of portable consumer electronic device, wideling popularize for new-energy automobile and building for smart grid
If society is further strong and eager for the demand of high-efficiency energy-storage equipment.Lithium ion battery is due to energy density height, memoryless effect
It answers, capacity usage ratio height, have extended cycle life and become the main force in existing energy storage device, but existing lithium ion battery energy is close
Degree has been approached theoretical limit, is not able to satisfy society gradually for the demand of high-energy density.With more high specific energy, safe two
Primary cell becomes whole society's focus of attention.New breakthrough needs are innovated from material system；Therefore, science researcher is again heavy
Newly sight is focused on the lithium metal battery field using lithium metal as cathode.Lithium metal, which is used as cathode, has natural advantage, than
Such as most negative electrode potential (- 3.040V), high theoretical capacity (3860mAh g-1), these special properties make lithium metal
The energy density of battery is likely to be breached 500Whkg-1, to meet growing social demand.
However, lithium metal battery, since the 1950s is suggested, in liquid electrolyte, lithium an- ode is always
It is faced with since lithium deposits uneven bring safety problem, hampers the commercialization of lithium metal battery.Compared to liquid electrolyte
Liquid, solid electrolyte has nonflammable, nonvolatile characteristic, and can effectively prevent battery short circuit, can significantly increase battery
Safety.Therefore, by the concern of scientific research personnel.2011, successfully developing ion conductance Japanese Scientists villous themedas wild time could
Match in excellence or beauty the sulphur system solid electrolyte of liquid electrolyte, and common people is allowed to see the application potential of solid electrolyte again.Sulphur removal system is solid
Outside state electrolyte, Garnet type, NASICON type solid electrolyte also ion conductance with higher can satisfy routine substantially
Requirement under operating condition.It is that " point-to-point " connects with the lithium an- ode way of contact however due to the solid-state properties of solid electrolyte
Touching, causes interface resistance to significantly increase, prevent battery under the conditions of room temperature and big multiplying power from working.In addition, existing anode
Material is mostly porous powder material, same when contacting with solid electrolyte to be faced with that contact area is small, interfacial resistance
Big problem greatly hampers the practicalization of solid electrolyte.Therefore, how to reduce solid state lithium battery interface resistance at
For the key of solid electrolyte functionization.
Summary of the invention
The purpose of the present invention is to provide a kind of solid state lithium batteries with low interfacial resistance, it is intended to enable battery normal
It is worked normally under warm and larger multiplying power, and improves the safety of solid state lithium battery.
Technical scheme is as follows:
A kind of solid state lithium battery with low interfacial resistance, the solid state lithium battery contain anode, inorganic solid electrolyte
And lithium anode, it is characterised in that: anode and inorganic solid electrolyte between and lithium anode and inorganic solid-state electricity
It is respectively present boundary moisture agent between solution matter, which contains ether-ether class mixed solvent and lithium salts, lithium salts molar concentration
For 1.0-2.5mol/L；The boundary moisture agent is formed as solid-state interface film after electrochemical in-situ is handled.
In above-mentioned technical proposal, it is characterised in that: anode and inorganic solid electrolyte between and lithium anode with
The usage amount of existing boundary moisture agent is 1-5 μ L/cm between inorganic solid electrolyte2。
The electrochemical process for treating of boundary moisture agent of the present invention are as follows: first constant-current charge to blanking voltage, then ending
Continue constant-voltage charge under voltage, then constant-current discharge；Current range is 0.01-0.1C when constant-current charge and constant-current discharge；It cuts
Only voltage range is 3.8-4.7V, and constant-voltage charge is until electric current is less than 0.05C.
The lithium salts that boundary moisture agent of the present invention uses is lithium nitrate, lithium hexafluoro phosphate, dioxalic acid lithium borate, double trifluoros
One of sulfonyl methane imine lithium, double fluorine sulfimide lithiums, lithium perchlorate, difluorine oxalic acid boracic acid lithium and trifluoromethanesulfonic acid lithium or
Several mixing；Preferably, the lithium salts that the boundary moisture agent uses must include lithium nitrate, and the molar concentration of lithium nitrate is 0.1-
1.0mol/L。
Preferably, ether-ether class in the mixed solvent used in the boundary moisture agent, ether solvent volume fraction are 30-
70%；The volume fraction of esters solvent is 30-70%.
Preferably, the esters solvent is dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, ethylene carbonate, fluorine
For the mixed solvent of one or more of ethylene carbonate, propene carbonate and trifluoro propene carbonic ester；Boundary moisture agent makes
Ether solvent is glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethyleneglycol dimethyl ether, two sweet
One or more of mixing of diethylene glycol dimethyl ether, triglyme and tetraethylene glycol dimethyl ether.
Inorganic solid electrolyte of the present invention is oxidized form inorganic solid electrolyte；The oxidized form inorganic solid-state electricity
Xie Zhiwei is selected from Li1+mAlmTi2-m(PO4)3And Li7-2n-jLa3Zr2-jMjO12One of；Wherein, 0≤m≤2,0≤n≤3,0
≤ j≤2, M are Nb and/or Ta.
Compared with prior art, the present invention having the following advantages that and high-lighting effect: the present invention uses a small amount of liquid electrolyte
Liquid is added separately between anode and solid electrolyte and between lithium anode and solid electrolyte as boundary moisture agent,
Then boundary moisture agent is made to become solid-state interface film by the method that electrochemical in-situ is handled.The present invention can significantly reduce in battery
The interface resistance of portion's anode and solid electrolyte and lithium anode and solid electrolyte, thus enable battery in room temperature and
It is worked normally under larger multiplying power, the safety of battery is obviously improved.Compatible a variety of oxidized form inorganic solid electrolytes,
There is versatility in a certain range.With wide electrochemical stability window, compatible high-voltage positive electrode material brings high-energy close
Degree.Using Li7La3Zr2O12It is the solid state lithium battery of anode for inorganic solid electrolyte, LiFePO4, at boundary moisture agent
After reason, coulombic efficiency is greater than 98%, in 50 circulating content amount conservation rates up to 90% or more.
Detailed description of the invention
Fig. 1 is a kind of principle schematic diagram of the solid state lithium battery with low interfacial resistance provided by the invention.
In figure: 1- lithium anode；2- boundary moisture agent；3- inorganic solid electrolyte；4- anode；5- external power supply.
Specific embodiment
A kind of solid state lithium battery with low interfacial resistance provided by the invention, the solid state lithium battery contain positive 4, nothing
Machine solid electrolyte 3 and lithium anode 1, anode 4 and inorganic solid electrolyte 3 between and lithium anode 1 with it is inorganic
Boundary moisture agent 2 is respectively present between solid electrolyte 3, which contains ether-ether class mixed solvent and lithium salts, lithium salts
Molar concentration is 1.0-2.5mol/L；The boundary moisture agent is formed as solid-state interface film after electrochemical in-situ is handled.It is described
Boundary moisture agent unilateral side usage amount be 1-5 μ L/cm2。
It the use of boundary moisture agent electrochemical process for treating is first constant-current charge to blanking voltage in above-mentioned technical proposal,
Continue constant-voltage charge under blanking voltage again, then constant-current discharge；Current range is 0.01-when constant-current charge and constant-current discharge
0.1C；Blanking voltage range is 3.8-4.7V, and constant-voltage charge is until electric current is less than 0.05C.
In the present invention, lithium salts used in the boundary moisture agent be lithium nitrate, lithium hexafluoro phosphate, dioxalic acid lithium borate,
In double trifluoromethanesulfonimide lithiums, double fluorine sulfimide lithiums, lithium perchlorate, difluorine oxalic acid boracic acid lithium and trifluoromethanesulfonic acid lithium
One or more of mixing；Preferably, the lithium salts that the boundary moisture agent uses must include lithium nitrate；The molar concentration of lithium nitrate
For 0.1-1.0mol/L.
The ether-ether class in the mixed solvent that boundary moisture agent of the present invention uses, preferably ether solvent volume fraction are
30-70%；The volume fraction of esters solvent is 30-70%.Esters solvent is dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate
The mixing of one or more of ester, ethylene carbonate, fluorinated ethylene carbonate, propene carbonate and trifluoro propene carbonic ester is molten
Agent；The ether solvent that boundary moisture agent uses is glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetrem
One or more of mixing of glycol dimethyl ether, diethylene glycol dimethyl ether, triglyme and tetraethylene glycol dimethyl ether.
In above-mentioned technical proposal, the inorganic solid electrolyte used is oxidized form inorganic solid electrolyte；The oxidation
Type inorganic solid electrolyte is selected from Li1+mAlmTi2-m(PO4)3And Li7-2n-jLa3Zr2-jMjO12One of；Wherein, 0≤m≤
2,0≤n≤3,0≤j≤2, M are Nb and/or Ta.
Below with reference to several specific examples, the present invention will be further described, but protection scope of the present invention is not limited to
Embodiment below.
First, in accordance with lithium anode, boundary moisture agent, inorganic solid electrolyte, boundary moisture agent, positive sequence group
Packed battery (hereinafter, is abbreviated as lithium metal/boundary moisture agent/inorganic solid electrolyte/boundary moisture agent/anode).Then, boundary
Face wetting agent becomes solid-state interface film after electrochemical in-situ is handled.
Embodiment 1: assembling lithium metal/boundary moisture agent/Li7La3Zr2O12/ boundary moisture agent/LiFePO4 solid-state knob
Button battery, 30 DEG C of test temperature.Boundary moisture agent group becomes fluorinated ethylene carbonate: diethyl carbonate: diethylene glycol dimethyl ether
=4:3:3 (volume ratio), contains 1.0mol/L lithium hexafluoro phosphate and 0.2mol/L lithium nitrate.Boundary moisture agent usage amount is every side
2μL/cm2.Electrochemical treatment process are as follows: first 0.05C constant-current charge to 3.8V, then constant-voltage charge to electric current is less than at 3.8V
0.05C, then 0.05C constant-current discharge are recycled 5 times.It is recycled at 0.1C after electrochemical treatments, in 50 circulations, capacity is protected
Holdup is 92%.
Embodiment 2: assembling lithium metal/boundary moisture agent/Li7La3Zr2O12/ boundary moisture agent/LiFePO4 solid-state knob
Button battery, 30 DEG C of test temperature.Boundary moisture agent group becomes fluorinated ethylene carbonate: diethylene glycol dimethyl ether=4:6 (volume
Than), contain the bis- trifluoromethanesulfonimide lithiums of 2.0mol/L and 0.5mol/L lithium nitrate.Boundary moisture agent usage amount is every 4 μ of side
L/cm2.Electrochemical treatment process are as follows: first 0.05C constant-current charge to 4.0V, then constant-voltage charge to electric current is less than at 4.0V
0.05C, then 0.05C constant-current discharge are recycled 5 times.It is recycled at 0.1C after electrochemical treatments, in 50 circulations, capacity is protected
Holdup is 95%.
Embodiment 3: assembling lithium metal/boundary moisture agent/Li1.5Al0.5Ti1.5(PO4)3/ boundary moisture agent/LiFePO4
Solid-state button cell, 30 DEG C of test temperature.Boundary moisture agent group becomes propene carbonate: diethyl carbonate: tetraethylene glycol diformazan
Ether=1:5:4 (volume ratio), containing the bis- trifluoromethanesulfonimide lithiums of 1.0mol/L, 0.5mol/L dioxalic acid lithium borate and
0.3mol/L lithium nitrate.Boundary moisture agent usage amount is every 2 μ L/cm of side2.Electrochemical treatment process are as follows: first 0.02C constant-current charge
To 4.0V, then at 4.0V, constant-voltage charge to electric current is less than 0.05C, then 0.02C constant-current discharge, recycles 5 times.After electrochemical treatments
It is recycled at 0.1C, in 50 circulations, capacity retention ratio 89%.
Embodiment 4: assembling lithium metal/boundary moisture agent/Li7La3Zr2O12/ boundary moisture agent/cobalt acid lithium solid-state button
Battery, 30 DEG C of test temperature.Boundary moisture agent group is as fluorinated ethylene carbonate: dimethyl carbonate: glycol dimethyl ether=
3.5:3.5:3 (volume ratio), contains 1.0mol/L difluorine oxalic acid boracic acid lithium and 0.5mol/L lithium nitrate.Boundary moisture agent usage amount
For every 3 μ L/cm of side2.Electrochemical treatment process are as follows: first 0.01C constant-current charge to 4.3V, then at 4.3V constant-voltage charge to electric current
Less than 0.05C, then 0.01C constant-current discharge, recycle 5 times.It recycles at 0.1C after electrochemical treatments, in 50 circulations, holds
Measuring conservation rate is 93%.
Embodiment 5: assembling lithium metal/boundary moisture agent/Li1.5Al0.5Ti1.5(PO4)3/ boundary moisture agent/LiFePO4
Solid-state button cell, 30 DEG C of test temperature.Boundary moisture agent group becomes fluorinated ethylene carbonate: tetraethyleneglycol dimethyl ether=3:7
(volume ratio) contains 1.0mol/L lithium nitrate.Boundary moisture agent usage amount is every 4 μ L/cm of side2.Electrochemical treatment process are as follows: first
To 4.0V, then at 4.0V, constant-voltage charge to electric current is less than 0.05C, then 0.05C constant-current discharge, circulation 5 to 0.05C constant-current charge
It is secondary.It is recycled at 0.1C after electrochemical treatments, in 50 circulations, capacity retention ratio 65%.
Embodiment 6: assembling lithium metal/boundary moisture agent/Li6.5La3Zr1.5Ta0.5O12/ boundary moisture agent/nickel cobalt lithium aluminate
Solid-state button cell, 30 DEG C of test temperature.Boundary moisture agent group becomes propene carbonate: diethyl carbonate: dimethyl carbonate:
Diethylene glycol dimethyl ether=4:1:1:4 (volume ratio), contains 1.0mol/L lithium hexafluoro phosphate and 0.8mol/L lithium nitrate.Interface profit
Humectant usage amount is every 4 μ L/cm of side2.Electrochemical treatment process are as follows: first 0.01C constant-current charge to 4.5V, then the constant pressure at 4.5V
Electric current is charged to less than 0.05C, then 0.01C constant-current discharge, is recycled 5 times.It recycles at 0.1C after electrochemical treatments, is followed at 50 times
In ring, capacity retention ratio 87%.
Embodiment 7: assembling lithium metal/boundary moisture agent/Li6.5La3Zr1.5Ta0.5O12/ boundary moisture agent/LiFePO4
Solid-state button cell, 30 DEG C of test temperature.Boundary moisture agent group becomes fluorinated ethylene carbonate: diethyl carbonate: tetraethylene glycol
Dimethyl ether=2:1:7 (volume ratio) contains the bis- fluorine sulfimide lithiums of 2.0mol/L and 0.2mol/L lithium nitrate.Boundary moisture agent makes
Dosage is every 5 μ L/cm of side2.Electrochemical treatment process are as follows: first 0.02C constant-current charge to 4.0V, then constant-voltage charge is extremely at 4.0V
Electric current is less than 0.05C, then 0.02C constant-current discharge, recycles 5 times.It is recycled at 0.1C after electrochemical treatments, in 50 circulations,
Its capacity retention ratio is 94%.
Embodiment 8: assembling lithium metal/boundary moisture agent/Li6.5La3Zr1.5Ta0.5O12/ boundary moisture agent/nickel cobalt lithium aluminate
Solid-state button cell, 30 DEG C of test temperature.Boundary moisture agent group becomes ethylene carbonate: diethylene glycol dimethyl ether=1:1 (body
Product ratio), containing 0.6mol/L difluorine oxalic acid boracic acid lithium, the bis- fluorine sulfimide lithiums of 0.6mol/L and 0.3mol/L lithium nitrate.Interface
Wetting agent usage amount is every 2 μ L/cm of side2.Electrochemical treatment process are as follows: first 0.02C constant-current charge to 4.3V, then the perseverance at 4.3V
Pressure charges to electric current less than 0.05C, then 0.02C constant-current discharge, recycles 5 times.It is recycled at 0.1C after electrochemical treatments, at 50 times
In circulation, capacity retention ratio 95%.
Embodiment 9: assembling lithium metal/boundary moisture agent/Li1.5Al0.5Ti1.5(PO4)3/ boundary moisture agent/nickel cobalt lithium aluminate
Solid-state button cell, 30 DEG C of test temperature.Boundary moisture agent group becomes trifluoro propene carbonic ester: diethyl carbonate: tetraethylene glycol
Dimethyl ether=2:5:3 (volume ratio), contains 1.0mol/L difluorine oxalic acid boracic acid lithium and 0.2mol/L lithium nitrate.Boundary moisture agent makes
Dosage is every 3 μ L/cm of side2.Electrochemical treatment process are as follows: first 0.05C constant-current charge to 4.7V, then constant-voltage charge is extremely at 4.7V
Electric current is less than 0.05C, then 0.05C constant-current discharge, recycles 5 times.It is recycled at 0.1C after electrochemical treatments, in 50 circulations,
Its capacity retention ratio is 60%.
Embodiment 10: assembling lithium metal/boundary moisture agent/Li7La3Zr2O12/ boundary moisture agent/nickel cobalt lithium aluminate solid-state
Button cell, 30 DEG C of test temperature.Boundary moisture agent group becomes trifluoro propene carbonic ester: diethyl carbonate: triethylene glycol diformazan
Ether=4:3:3 (volume ratio) contains the bis- fluorine sulfimide lithiums of 1.5mol/L.Boundary moisture agent usage amount is every 2 μ L/cm of side2.Electricity
Chemical treating process are as follows: first 0.02C constant-current charge to 4.5V, then constant-voltage charge to electric current is less than 0.05C at 4.5V, then
0.02C constant-current discharge recycles 5 times.It is recycled at 0.1C after electrochemical treatments, in 50 circulations, capacity retention ratio is
74%.
Embodiment 11: assembling lithium metal/boundary moisture agent/Li7La3Zr2O12/ boundary moisture agent/nickel cobalt lithium aluminate solid-state
Button cell, 30 DEG C of test temperature.Boundary moisture agent group becomes fluorinated ethylene carbonate: methyl ethyl carbonate: tetraethylene glycol diformazan
Ether=4:2:4 (volume ratio) contains the bis- fluorine sulfimide lithiums of 2.0mol/L and 0.2mol/L lithium nitrate.Boundary moisture agent usage amount
For every 2 μ L/cm of side2.Electrochemical treatment process are as follows: first 0.1C constant-current charge to 4.3V, then at 4.3V constant-voltage charge to electric current
Less than 0.05C, then 0.1C constant-current discharge, recycle 5 times.It is recycled at 0.1C after electrochemical treatments, in 50 circulations, capacity
Conservation rate is 81%.
Embodiment 12: assembling lithium metal/boundary moisture agent/Li1.5Al0.5Ti1.5(PO4)3/ boundary moisture agent/cobalt acid lithium
Solid-state button cell, 30 DEG C of test temperature.Boundary moisture agent group becomes fluorinated ethylene carbonate: dimethyl carbonate: diethylene glycol (DEG) two
Methyl ether=3:3:4 (volume ratio), contains 1.5mol/L lithium hexafluoro phosphate and 0.2mol/L lithium nitrate.Boundary moisture agent usage amount is
Every side 3
μL/cm2.Electrochemical treatment process are as follows: first 0.1C constant-current charge to 4.2V, then at 4.2v constant-voltage charge to electric current
Less than 0.05C, then 0.1C constant-current discharge, recycle 5 times.It is recycled at 0.1C after electrochemical treatments, in 50 circulations, capacity
Conservation rate is 73%.
Embodiment 13: assembling lithium metal/boundary moisture agent/Li6.5La3Zr1.5Ta0.5O12/ boundary moisture agent/nickel cobalt aluminic acid
The solid-state button cell of lithium, 30 DEG C of test temperature.Boundary moisture agent group becomes ethylene carbonate: methyl ethyl carbonate: triethylene glycol two
Methyl ether=3:4:3 (volume ratio) contains the bis- fluorine sulfimide lithiums of 2.0mol/L and 0.1mol/L lithium nitrate.Boundary moisture agent uses
Amount is every 3 μ L/cm of side2.Electrochemical treatment process are as follows: first 0.1C constant-current charge to 4.3V, then at 4.3V constant-voltage charge to electricity
Stream is less than 0.05C, then 0.1C constant-current discharge, recycles 5 times.It recycles at 0.1C after electrochemical treatments, in 50 circulations, holds
Measuring conservation rate is 75%.
Embodiment 14: assembling lithium metal/boundary moisture agent/Li6.5La3Zr1.5Ta0.5O12/ boundary moisture agent/LiFePO4
Solid-state button cell, 30 DEG C of test temperature.Boundary moisture agent group becomes fluorinated ethylene carbonate: dimethyl carbonate: diethyl two
Diethylene glycol dimethyl ether=5:2:3 (volume ratio) contains the bis- trifluoromethanesulfonimide lithiums of 0.6mol/L, the bis- fluorine sulfimides of 0.6mol/L
Lithium and 0.2mol/L lithium nitrate.Boundary moisture agent usage amount is every 3 μ L/cm of side2.Electrochemical treatment process are as follows: first 0.05C constant current
4.0V is charged to, then constant-voltage charge to electric current is less than 0.05C, then 0.05C constant-current discharge at 4.0V, recycles 5 times.At electrochemistry
It is recycled at 0.1C after reason, in 50 circulations, capacity retention ratio 88%.
Embodiment 15: assembling lithium metal/boundary moisture agent/Li6.5La3Zr1.5Ta0.5O12/ boundary moisture agent/LiFePO4
Solid-state button cell, 60 DEG C of test temperature.Boundary moisture agent group becomes ethylene carbonate: triethylene glycol dimethyl ether=3:7 (body
Product ratio), contain 1.0mol/L trifluoromethanesulfonic acid lithium and 1.0mol/L lithium nitrate.Boundary moisture agent usage amount is every 2 μ L/cm of side2。
Electrochemical treatment process are as follows: first 0.02C constant-current charge to 4.0V, then constant-voltage charge to electric current is less than 0.05C at 4.0V, then
0.02C constant-current discharge recycles 5 times.It is recycled at 0.1C after electrochemical treatments, in 50 circulations, capacity retention ratio is
76%.
Embodiment 16: assembling lithium metal/boundary moisture agent/Li1.5Al0.5Ti1.5(PO4)3/ boundary moisture agent/LiFePO4
Solid-state button cell, 60 DEG C of test temperature.Boundary moisture agent group becomes ethylene carbonate: methyl ethyl carbonate: triethylene glycol two
Methyl ether=4:1:5 (volume ratio), containing 0.5mol/L lithium hexafluoro phosphate, the bis- fluorine sulfimide lithiums of 0.5mol/L and 0.3mol/L nitre
Sour lithium.Boundary moisture agent usage amount is every 2 μ L/cm of side2.Electrochemical treatment process are as follows: first 0.05C constant-current charge to 4.2V, then
Constant-voltage charge to electric current is less than 0.05C, then 0.05C constant-current discharge at 4.2v, recycles 5 times.After electrochemical treatments at 0.1C
Circulation, in 50 circulations, capacity retention ratio 90%.
Embodiment 17: assembling lithium metal/boundary moisture agent/Li7La3Zr2O12/ boundary moisture agent/LiFePO4 solid-state knob
Button battery, 60 DEG C of test temperature.Boundary moisture agent group becomes trifluoro propene carbonic ester: diethyl carbonate: tetraethyleneglycol dimethyl ether
=3:2:5 (volume ratio) contains the bis- fluorine sulfimide lithiums of 2.0mol/L and 0.2mol/L lithium nitrate.Boundary moisture agent usage amount is
Every 4 μ L/cm of side2.Electrochemical treatment process are as follows: first 0.02C constant-current charge to 4.0V, then constant-voltage charge is small to electric current at 4.0V
In 0.05C, then 0.02C constant-current discharge, recycle 5 times.It is recycled at 0.1C after electrochemical treatments, in 50 circulations, capacity
Conservation rate is 93%.
Claims (8)
1. a kind of solid state lithium battery with low interfacial resistance, the solid state lithium battery contain anode, inorganic solid electrolyte and
Lithium anode, it is characterised in that: between anode and inorganic solid electrolyte and lithium anode is electrolysed with inorganic solid-state
Boundary moisture agent is respectively present between matter, which contains ether-ether class mixed solvent and lithium salts, and lithium salts molar concentration is
1.0–2.5mol/L；The boundary moisture agent is formed as solid-state interface film after electrochemical in-situ is handled.
2. a kind of solid state lithium battery with low interfacial resistance as described in claim 1, it is characterised in that: anode with it is inorganic
The usage amount of existing boundary moisture agent is 1-between solid electrolyte and between lithium anode and inorganic solid electrolyte
5μL/cm2。
3. a kind of solid state lithium battery with low interfacial resistance as described in claim 1, it is characterised in that: the boundary moisture agent
Electrochemical process for treating are as follows: first constant-current charge to blanking voltage, then continue constant-voltage charge under blanking voltage, then constant current is put
Electricity；Current range is 0.01-0.1C when constant-current charge and constant-current discharge；Blanking voltage range is 3.8-4.7V, constant-voltage charge
Until electric current is less than 0.05C.
4. a kind of solid state lithium battery with low interfacial resistance as claimed in claim 1,2 or 3, it is characterised in that: the lithium
Salt is lithium nitrate, lithium hexafluoro phosphate, dioxalic acid lithium borate, double trifluoromethanesulfonimide lithiums, double fluorine sulfimide lithiums, perchloric acid
The mixing of one or more of lithium, difluorine oxalic acid boracic acid lithium and trifluoromethanesulfonic acid lithium.
5. a kind of solid state lithium battery with low interfacial resistance as claimed in claim 1,2 or 3, it is characterised in that: the boundary
Contain lithium nitrate and lithium hexafluoro phosphate, dioxalic acid lithium borate, double trifluoromethanesulfonimide lithiums, double fluorine sulphurs in the wetting agent of face
The mixing of one or more of imide li, lithium perchlorate, difluorine oxalic acid boracic acid lithium and trifluoromethanesulfonic acid lithium；Lithium nitrate rubs
Your concentration is 0.1-1.0mol/L.
6. a kind of solid state lithium battery with low interfacial resistance as described in claim 1, it is characterised in that: the ether-ether class
In the mixed solvent, ether solvent volume fraction are 30-70%；The volume fraction of esters solvent is 30-70%.
7. a kind of solid state lithium battery with low interfacial resistance as claimed in claim 6, be: the esters solvent is
Dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, ethylene carbonate, fluorinated ethylene carbonate, propene carbonate and trifluoropropyl
The mixed solvent of one or more of olefinic carbon acid esters；The ether solvent be glycol dimethyl ether, diethylene glycol dimethyl ether,
Triethylene glycol dimethyl ether, tetraethyleneglycol dimethyl ether, diethylene glycol dimethyl ether, triglyme and tetraethylene glycol dimethyl ether one kind or
Several mixing.
8. a kind of solid state lithium battery with low interfacial resistance as described in claim 1, it is characterised in that: described is inorganic solid
State electrolyte is oxidized form inorganic solid electrolyte；The oxidized form inorganic solid electrolyte is selected from Li1+mAlmTi2-m(PO4)3
And Li7-2n-jLa3Zr2-jMjO12One of；Wherein, 0≤m≤2,0≤n≤3,0≤j≤2, M are Nb and/or Ta.
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