CN106876707A - A kind of solid lithium battery - Google Patents
A kind of solid lithium battery Download PDFInfo
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- CN106876707A CN106876707A CN201710216318.7A CN201710216318A CN106876707A CN 106876707 A CN106876707 A CN 106876707A CN 201710216318 A CN201710216318 A CN 201710216318A CN 106876707 A CN106876707 A CN 106876707A
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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- H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
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Abstract
The present invention provides a kind of solid lithium battery, including positive pole, negative pole and the solid electrolyte between positive pole and negative pole, it is characterised in that the main component in the solid electrolyte is LiM2(PO4)3Based compound, the main component in the positive pole is Li3V2(PO4)3Based compound and LiM2(PO4)3One or more in based compound, wherein M=Ge, Ti, Hf, Al, Si, V, Sc or Zr；The Li3V2(PO4)3Based compound and LiM2(PO4)3Based compound is NASICON structures.The present invention is by using the solid electrolyte and positive pole for being all NASICON structures so that the structure matching degree of solid electrolyte and positive pole is improved, and greatly reduces interface resistance so that the combination property of solid lithium battery gets a promotion.
Description
【Technical field】
The invention belongs to electrokinetic cell field, and in particular to a kind of solid lithium battery.
【Background technology】
It is in recent years increasingly reducing for the global non-renewable energy resources petroleum reserves of reply and continuing for global warming gas
It is soaring, natural resources for the survival of mankind and natural environment are protected, various countries will develop new energy and new-energy automobile one after another
Selected as the grand strategy of national development.Lithium ion battery as a kind of important energy storage device, because it has operating voltage
It is high, that energy density is big, self discharge is small, have extended cycle life, temperature in use wide ranges, memory-less effect, security performance are protruded etc. is excellent
Point, has been widely used in the conventional small field of batteries such as camera, mobile phone, notebook computer, and just towards big
The power battery of electric motor car and wind energy of type and the energy-storage battery direction of the sun are developed, and this is proposed more to its security performance
Big challenge.
Conventional commercial lithium ion battery mainly uses the liquid electrolyte containing flammable organic solvent, there is serious safety
Hidden danger, when lithium ion battery because when any reason is short-circuit, battery self-energy can in the form of heat be discharged in the short time, just
The serious security incidents such as on fire or even blast may occur.Additionally, electrolyte can occur side reaction with electrode material, cause electricity
There is irreversible decay in tankage, while also bringing along the problems such as flatulence, leakage.At present, many researchers mainly use
The modes such as additive are added to be improved organic electrolyte in the electrolytic solution, to solve the security of liquid lithium ionic cell
Problem.Though this achieves some achievements, the safety issue of electrokinetic cell can not be fundamentally solved.The presence of these problems
The use of lithium ion battery is limited, its huge barrier in the future in terms of electrokinetic cell and Large Copacity stored energy application is also become
Hinder.In order to thoroughly solve the problems, such as lithium ion battery security, a kind of brand-new lithium ion battery --- solid lithium battery enters
The sight line of people.
Relative to traditional liquid lithium battery, solid state lithium battery replaces traditional liquid organic electrolyte with solid electrolyte,
Can overcome due to the problems such as security performance is low, cycle life is short, operating temperature range is narrow caused by liquid electrolyte.Solid-state electricity
Solution matter also functions as the role of barrier film except conducting lithium ions, thus preferably lithium ion solid electrolyte should have it is good from
Electron conductivity, extremely low electronic conductivity, minimum grain boundary resistance, and chemical stability is good, thermal coefficient of expansion and electrode material
Match, electrochemical decomposition voltage is high.
NASICON (sodium super ion conductors) structure type fast-ionic conductor is that a class is ground extensively
The solid electrolyte material studied carefully, the molecular formula of this kind of compound is generally M [A2B3O12], wherein M, A, B represent monovalence, four respectively
The cation of valency and pentavalent, its skeleton structure is by AO6Octahedra and BO4Tetrahedron is collectively forming, and belongs toSpace group.
In this configuration, M+Conductive ion can take up two kinds of interstitial positions, i.e. MI octahedral interstices and MII tetrahedrons space.By
It is lower than MII in the potential energy of MI, therefore MI by M+All take, usual MII is not occupied then, so, in NASICON knots
In structure, M+The migration path of ion has two kinds：A kind of is that, by MI → MII transition of MIMII bottlenecks, another kind is to pass through
MII → MII transition of MIIMII bottlenecks.Directly replace the Li for obtaining3Zr2Si2PO12It is a kind of lithium ion battery solid electrolyte,
But due to Na3Zr2Si2PO12Originally it is adapted to Na in structure+The transmission channel size of migration is with respect to Li+It is too big, be not suitable for Li+'s
Migration, so lithium ion conductivity is very low, compared with Na3Zr2Si2PO12Low about three orders of magnitude of sodium ion electrical conductivity.By with not
Ion-pair structure skeleton ion with size is replaced, and then changes transmission channel size, can obtain lithium ion conductivity
To lifting.Wherein, Zr4+Can be by Ti4+、Ge4+、Hf4+、V5+Or Sc3+Substitution, the compound after substitution is still tied with NASICON
Structure, and the lithium ion conductivity of material is greatly improved.
It is generally believed that the key factor of restriction solid lithium battery performance has two aspects：One is inorganic solid electrolyte material
The ionic conductivity of material itself, two is the interface in solid lithium battery.By substantial amounts of research, have been able to prepare at present
The solid electrolyte of the conductivity at room temperature rate high compared favourably with liquid electrolyte, but solid electrolyte and positive electrode interface still
With impedance higher, there is obvious grain boundary effect, be the principal element for limiting solid state lithium battery performance.
【The content of the invention】
It is an object of the invention to provide a kind of solid lithium battery, interface resistance can be reduced so that all solid lithium electricity
The combination property in pond gets a promotion.
The technical scheme is that：
A kind of solid lithium battery, including positive pole, negative pole and the solid electrolyte between positive pole and negative pole, it is special
Levy and be, the main component in the solid electrolyte is LiM2(PO4)3Based compound, the main component in the positive pole is
Li3V2(PO4)3Based compound and LiM2(PO4)3One kind in based compound, wherein M=Ge, Ti, Hf, Al, Si, V, Sc or Zr
Or it is several；The Li3V2(PO4)3Based compound and LiM2(PO4)3Based compound is NASICON structures.The technical scheme is led to
Solid electrolyte and positive pole are crossed using structure identical NASICON compounds, construct the solid electrolyte of structure matching with just
Pole material, thus lithium ion is not between larger electrochemistry potential difference, this causes solid electrolyte and positive pole material
The interface resistance of material is greatly improved；Simultaneously because structure is identical, migrating channels of the lithium ion in charge and discharge process
Crystal structure is consistent, is more beneficial for the migration of lithium ion, greatly reduces interface resistance so that the synthesis of solid lithium battery
Performance gets a promotion.
Further, above-mentioned LiM2(PO4)3Based compound is Li1+xAlxTi2-x(PO4)3(abbreviation LATP) or Li1+ xAlxGe2-x(PO4)3(abbreviation LAGP), wherein 0≤x≤1.Li1+xAlxTi2-x(PO4)3Or Li1+xAlxGe2-x(PO4)3Not only
It is safe, and the size of lithium ion mobility passage in lattice is changed, the raising to crystal grain ionic conductivity is favourable, Li1+ xAlxGe2-x(PO4)3Also there is more stable chemical property between 1.0-6.0V, electrochemical window scope is bigger.
Further, above-mentioned LiM2(PO4)3Based compound is the compound that Si or B or Fe adulterates, and doping changes lattice
The size of middle lithium ion mobility passage, improves ionic conductivity, improves the overall performance of battery.
Further, above-mentioned Li3V2(PO4)3Based compound is the Li of C claddings3V2(PO4)3Base active material.Coated using C
Li3V2(PO4)3Base active material, can further improve the electronic conductivity of material, while suppressing vanadium in the electrolytic solution
Dissolving.
Further, above-mentioned positive pole also includes conductive agent.Conductive agent is added, has built electronic conduction network, can improve just
Electron conduction between the active component of pole and between active component and collector.
Further, above-mentioned conductive agent is conductive black (including super P, SP-Li, Ketjen black, acetylene black etc.), conduction
One kind in graphite (including KS-6, KS-15, SFG-6, SFG-15 etc.), Graphene, carbon fiber, CNT or fullerene
Or it is several.
Further, the Li in the positive pole3V2(PO4)3Based compound and LiM2(PO4)3The mass ratio of based compound is
9:(1~9).Too high electrolyte content, reduces the energy density of battery, the interface impedance of too low electrolyte content then battery
Greatly, battery polarization is larger, influences the capacity of material to play.
Further, the content of above-mentioned conductive agent is Li3V2(PO4)3Based compound and LiM2(PO4)3Based compound quality
The 1~10% of sum.Conductive agent content is too low, and electronic conduction is poor；Too high levels, energy density reduction.
Further, above-mentioned solid electrolyte is the laminated structure that thickness is 50~500 microns, the sheet solid-state of the thickness
Electrolyte can both serve as the role of barrier film, and lithium ion can be effectively conducted again.
The technical scheme has following beneficial technique effect：
1) technical scheme is by using the solid electrolyte and positive pole for being all NASICON structures, constructing structure matching
Solid electrolyte and positive electrode, thus lithium ion is not between larger electrochemistry potential difference, and this causes solid
The interface resistance of body electrolyte and positive electrode is greatly improved；Simultaneously because structure is identical, lithium ion is in discharge and recharge
The crystal structure of the migrating channels in journey is consistent, is more beneficial for the migration of lithium ion, greatly reduces interface resistance so that complete
The combination property (such as cycle performance, charge-discharge performance) of solid state lithium battery gets a promotion.
2) technical scheme is by using being all the solid electrolyte and positive pole of NASICON structures, it is to avoid electrolyte
While oxidation Decomposition, the operating voltage for also improving lithium battery is interval, can further improve the energy density of lithium battery.Mesh
The antidecomposition voltage of liquid electrolyte is generally less than 4.5V in preceding ripe commercial lithium battery, although have various high-voltage electrolytes
It is in research and development but still immature；If using existing ripe liquid electrolyte, Li3V2(PO4)3Based active material or
Ni-Mn high voltage systems cannot give play to its high-tension advantage；And using the solid electrolyte for being all NASICON structures and just
Pole, typically all has the electrochemical window higher than 5V, and positive electrode active materials can be made greatly to have given play to its high-tension advantage.
3) technical scheme passes through Li3V2(PO4)3Based compound and LiM2(PO4)3Based compound is used cooperatively, room temperature from
Electron conductivity is improved, and solid lithium battery can be made to be operated at room temperature, solves organic solid electrolyte or multiple
The problem that solid electrolyte needs to be used in the temperature (such as 60 DEG C or so) more than room temperature is closed, is conducive to improving the design of lithium battery
And application；
4) solid lithium battery of the structure can be assembled by stacked mode, and process is simple is widely used, it is easy to
Promote.
【Brief description of the drawings】
Fig. 1 is the XRD spectrum of the solid electrolyte LATP in embodiment one；
Fig. 2 is assembling flow path figure (the mark explanation of solid lithium battery of the invention：1, solid electrolyte flake；2, just
Pole；3, negative pole；4, aluminium foil；5, Copper Foil；6, lug)；
Fig. 3 is the surface SEM figures of the solid electrolyte LATP in embodiment one；
Fig. 4 is interracial contact SEM figures (the red line mark of the solid electrolyte LATP thin slices in embodiment one and anode composite
Scope be anode composite thickness, about 20 μm)；
Fig. 5 is the charge-discharge performance test chart of the circulation 10 times, 15 times and 20 times of the solid lithium battery in embodiment one；
Fig. 6 is the cycle performance and coulombic efficiency test chart of the solid lithium battery in embodiment one；
Fig. 7 is that the positive pole of the solid lithium battery in embodiment one is composed with the interface impedance of solid electrolyte；
Fig. 8 is the cycle performance and coulombic efficiency test chart of the solid lithium battery in embodiment two；
Fig. 9 is the cycle performance and coulombic efficiency test chart of the solid lithium battery in embodiment three；
Figure 10 is the first charge-discharge curve of the all-solid-state battery in comparative example one；
Figure 11 is that the positive pole of the solid lithium battery in comparative example one is composed with the interface impedance of solid electrolyte；
Figure 12 is the cycle performance and coulombic efficiency test chart of the solid lithium battery in comparative example two；
Figure 13 is that the positive pole of the solid lithium battery in comparative example two is composed with the interface impedance of solid electrolyte.
【Specific embodiment】
Below in conjunction with specific embodiment, the present invention is described further.
Embodiment provided below is simultaneously not used to the scope that the limitation present invention is covered, described step nor with
To limit its execution sequence.Those skilled in the art do conspicuously improved with reference to existing common knowledge to the present invention, also fall
Enter within the protection domain of application claims.
Embodiment one
A kind of solid lithium battery, including positive pole 2, negative pole 3 and the solid electrolyte between positive pole 2 and negative pole 3.
Solid electrolyte use the NASICON structure solids electrolyte sheet 1 of 300 microns of thickness, its XRD spectrum as shown in figure 1,
Main component is that principal crystalline phase is LiGe2(PO4)3Li1.5Al0.5Ge1.5(PO4)3(referred to as LAGP, similarly hereinafter), corresponding to PDF#
80-1924.The Li of the C claddings of 80 parts by weight that positive pole is used3V2(PO4)3, LAGP and 2 part of 20 parts by weight of carbon black leads
Electric agent.
The solid lithium battery of the present embodiment is prepared (flow chart is as shown in Figure 2) by following technique：
(1) the LAGP solid electrolyte flakes 1 that thickness is 300 μm are taken, size is 4cm × 4cm, and conductivity at room temperature reaches
To 4 × 10-4S/cm；
(2) Li for coating C3V2(PO4)3With LAGP solid electrolytes according to 8:2 ratio mixing, and add first two
The conductive black of the 2% of material mass sum prepares anode composite；The anode composite of 10mg or so is taken, the N- methyl of 5mg is added
Pyrrolidones (NMP) is configured to slurry, and slurry is uniformly coated on solid electrolyte flake 1 using silk-screen printing, 60 DEG C
Drying 24h, forms combination electrode；
(3) after drying, be coated with the electrolyte sheet of anode composite under Ar gas atmosphere, 400 DEG C for the treatment of 2h, formed with
The positive pole 2 that solid electrolyte flake 1 is combined；
(4) opposite side that Li-In alloys are affixed on solid electrolyte is formed into negative pole 3 in glove box after being disposed, and
Aluminium foil 4 and Copper Foil 5 are placed as collector in positive pole 2 and the side of negative pole 3 respectively, lug 6 is drawn, by electricity by the way of thermoplastic envelope
Pond is fixed and finishes and realize the isolation with air.
Microstructure to the LAGP solid electrolytes of the present embodiment is observed, as shown in Figure 3 and Figure 4, LAGP solids
What electrolyte was formed is the primary particle of 300~500nm or so, and the scope of red line mark is the thickness of positive pole, about 20 microns, right
The interface impedance of battery is tested, and its result is as shown in figure 5, interface impedance about 8m Ω m at room temperature2。
Under 0.2C multiplying powers, the cycle performance of all-solid-state battery and the charge-discharge performance test to assembling, such as Fig. 5 and Tu
Shown in 6, as a result show, circulate beyond 100 times, the capacity of lithium battery is maintained at more than 90mAh/g, and cyclical stability is preferable, storehouse
Human relations efficiency is maintained essentially at more than 95%.
Embodiment two
A kind of solid lithium battery, including positive pole, negative pole and the solid electrolyte between positive pole and negative pole.Solid
Electrolyte uses the NASICON structure solid electrolyte sheets of 200 microns of thickness, and main component is that principal crystalline phase is LiTi2
(PO4)3Li1.3Al0.3Ti1.7(PO4)3(referred to as LATP, similarly hereinafter).The Li of the C claddings of 75 parts by weight that positive pole is used3V2
(PO4)3, the LATP of 25 parts by weight, 1 part of graphite agent and 1 part of carbon nanotube conducting agent.
The solid lithium battery of the present embodiment is prepared by following technique：
(1) the LATP solid electrolyte flakes that thickness is 200 μm are taken, size is 2cm × 2cm, and conductivity at room temperature reaches
To 8 × 10-4S/cm；
(2) Li for coating C3V2(PO4)3With LATP solid electrolytes according to 75:25 ratio mixing, and add preceding two
The conductive agent for planting the 2% of material mass sum prepares anode composite；The anode composite of 3mg or so is taken, adds the ethyl of 1.4mg fine
The solvent that dimension element and terpinol etc. have been configured prepares slurry, slurry is uniformly coated in solid electrolyte using silk-screen printing thin
On piece, 65 degree of drying 24h；
(3) after drying, the electrolyte sheet of anode composite is coated with Ar gas atmosphere, 400 DEG C process 2h；
(4) Li-In alloys are affixed on the opposite side of solid electrolyte after being disposed in glove box, and respectively in positive pole
Aluminium foil and Copper Foil are placed as collector with negative side, lug is drawn, and battery is fixed finishing and real by the way of thermoplastic envelope
Now with the isolation of air.
Under 0.2C multiplying powers, the cycle performance of all-solid-state battery and the charge-discharge performance test to assembling, such as Fig. 8 institutes
Show, as a result show, circulate beyond 100 times, the capacity of lithium battery is maintained at 100mAh/g or so.
Embodiment three
A kind of solid lithium battery, including positive pole, negative pole and the solid electrolyte between positive pole and negative pole.Solid
Electrolyte uses the NASICON structure solid electrolyte sheets of the Si doping of 500 microns of thickness, and main component is principal crystalline phase
It is LiGe2(PO4)3Li1.52Al0.5Ge1.5Si0.02P2.98O12(referred to as LAGSP, similarly hereinafter).70 parts by weight that positive pole is used
Li3V2(PO4)3, LAGSP and 2 part of 30 parts by weight of carbon nanotube conducting agent.
The solid lithium battery of the present embodiment is prepared by following technique：
(1) the LAGSP solid electrolyte flakes that thickness is 500 μm are taken, size is 5cm × 5cm, and conductivity at room temperature reaches
To 6 × 10-4S/cm；
(2) by Li3V2(PO4)3With LAGSP solid electrolytes according to 70:30 ratio mixing, and add first two material
The conductive agent of the 10% of quality sum --- CNT, prepares anode composite；The anode composite of 16mg or so is taken, 8mg is added
The solvent that has configured such as NMP prepare slurry, slurry is uniformly coated on solid electrolyte flake using silk-screen printing, 60
Degree drying 24h；
(3) after drying, the electrolyte sheet of anode composite is coated with Ar gas atmosphere, 400 DEG C process 2h；
(4) Li-In alloys are affixed on the opposite side of solid electrolyte after being disposed in glove box, and respectively in positive pole
Aluminium foil and Copper Foil are placed as collector with negative side, lug is drawn, and battery is fixed finishing and real by the way of thermoplastic envelope
Now with the isolation of air.
Under 0.2C multiplying powers, the cycle performance of all-solid-state battery and the charge-discharge performance test to assembling, such as Fig. 9 institutes
Show, as a result show, circulate beyond 100 times, the capacity of lithium battery is maintained at 100mAh/g or so.
Example IV
A kind of solid lithium battery, including positive pole, negative pole and the solid electrolyte between positive pole and negative pole.Solid
Electrolyte uses the NASICON structure solid electrolyte sheets of the B doping of 50 microns of thickness, and main component is that principal crystalline phase is
Li1.02Ge2B0.02P3O12(referred to as LGBP, similarly hereinafter).The Li of 90 parts by weight that positive pole is used3V2(PO4)3, 10 parts by weight
LGBP and 10 part of graphene conductive agent.
The solid lithium battery of the present embodiment is prepared by following technique：
(1) the LGBP solid electrolyte flakes that thickness is 50 μm are taken, size is 5cm × 5cm, and conductivity at room temperature reaches
6.1×10-4S/cm；
(2) by Li3V2(PO4)3With LGBP solid electrolytes according to 90:10 ratio mixing, and add first two material matter
Conductive agent --- the Graphene of the 10% of amount sum, prepares anode composite；The anode composite of 16mg or so is taken, the NMP of 8mg is added
Slurry is prepared Deng the solvent for having configured, slurry is uniformly coated on solid electrolyte flake using silk-screen printing, 60 degree of bakings
Dry 24h；
(3) after drying, the electrolyte sheet of anode composite is coated with Ar gas atmosphere, 400 DEG C process 2h；
(4) Li-In alloys are affixed on the opposite side of solid electrolyte after being disposed in glove box, and respectively in positive pole
Aluminium foil and Copper Foil are placed as collector with negative side, lug is drawn, and battery is fixed finishing and real by the way of thermoplastic envelope
Now with the isolation of air.
Under 0.2C multiplying powers, as a result the cycle performance of all-solid-state battery and the charge-discharge performance test to assembling show,
Circulate beyond 100 times, the capacity of lithium battery is maintained at 110mAh/g or so.
Embodiment five
A kind of solid lithium battery, including positive pole, negative pole and the solid electrolyte between positive pole and negative pole.Solid
Electrolyte uses the NASICON structure solid electrolyte sheets of the Fe doping of 400 microns of thickness, and main component is principal crystalline phase
It is Li2.02AlTiFe0.02P3O12(referred to as LATFP, similarly hereinafter).The Li of 50 parts by weight that positive pole is used3V2(PO4)3, 50 weight
The electric conduction of carbon fiber agent of LGBP and 1 part of number.
The solid lithium battery of the present embodiment is prepared by following technique：
(1) the LATFP solid electrolyte flakes that thickness is 400 μm are taken, size is 5cm × 5cm, and conductivity at room temperature reaches
To 6.5 × 10-4S/cm；
(2) by Li3V2(PO4)3With LATFP solid electrolytes according to 50:50 ratio mixing, and add first two material
The conductive agent of the 1% of quality sum --- carbon fiber, prepares anode composite；The anode composite of 16mg or so is taken, adds 8mg's
The solvent that NMP etc. has been configured prepares slurry, is uniformly coated on solid electrolyte flake slurry using silk-screen printing, 60 degree
Drying 24h；
(3) after drying, the electrolyte sheet of anode composite is coated with Ar gas atmosphere, 400 DEG C process 2h；
(4) Li-In alloys are affixed on the opposite side of solid electrolyte after being disposed in glove box, and respectively in positive pole
Aluminium foil and Copper Foil are placed as collector with negative side, lug is drawn, and battery is fixed finishing and real by the way of thermoplastic envelope
Now with the isolation of air.
Under 0.2C multiplying powers, as a result the cycle performance of all-solid-state battery and the charge-discharge performance test to assembling show,
Circulate beyond 100 times, the capacity of lithium battery is maintained at 100mAh/g or so.
Embodiment six
A kind of solid lithium battery, including positive pole, negative pole and the solid electrolyte between positive pole and negative pole.Solid
Electrolyte uses the NASICON structure solid electrolyte sheets of the Si doping of 100 microns of thickness, and main component is principal crystalline phase
It is LiGe2(PO4)3Li1.52Sc0.5Ge1.5Si0.02P2.98O12(referred to as LSGSP, similarly hereinafter).60 parts by weight that positive pole is used
Li3V2(PO4)3With the LSGSP of 40 parts by weight.
The solid lithium battery of the present embodiment is prepared by following technique：
(1) the LSGSP solid electrolyte flakes that thickness is 100 μm are taken, size is 5cm × 5cm, and conductivity at room temperature reaches
To 6 × 10-4S/cm；
(2) by Li3V2(PO4)3With LSGSP solid electrolytes according to 60:40 ratio mixing, prepares anode composite；Take
The anode composite of 16mg or so, the solvent for adding NMP of 8mg etc. to configure prepares slurry, using silk-screen printing that slurry is uniform
Be coated on solid electrolyte flake, 60 degree drying 24h；
(3) after drying, the electrolyte sheet of anode composite is coated with Ar gas atmosphere, 400 DEG C process 2h；
(4) Li-In alloys are affixed on the opposite side of solid electrolyte after being disposed in glove box, and respectively in positive pole
Aluminium foil and Copper Foil are placed as collector with negative side, lug is drawn, and battery is fixed finishing and real by the way of thermoplastic envelope
Now with the isolation of air.
Under 0.2C multiplying powers, as a result the cycle performance of all-solid-state battery and the charge-discharge performance test to assembling show,
Circulate beyond 100 times, the capacity of lithium battery is maintained at 100mAh/g or so.
Comparative example one
With the LiFePO that there is C to coat in the prior art4As positive pole, using the LAGP of same embodiment one as solid electrolytic
Matter, lithium battery is prepared by following technique：
(1) the LAGP solid electrolyte flakes that thickness is 300 μm are taken, size is 4cm × 4cm, and conductivity at room temperature reaches
To 4 × 10-4S/cm；
(2) LiFePO for coating C4With LAGP solid electrolytes according to 8:2 ratio mixing, and add first two material
The conductive black of the 2% of quality sum prepares anode composite；The anode composite of 10mg or so is taken, the N- methylpyrroles of 5mg are added
Alkanone (NMP) is configured to slurry, is uniformly coated on solid electrolyte flake slurry using silk-screen printing, 60 DEG C of drying
24h；
(3) after drying, the electrolyte sheet of anode composite is coated with Ar gas atmosphere, 400 DEG C process 2h.
(4) Li-In alloys are affixed on the opposite side of solid electrolyte after being disposed in glove box, and respectively compound
Positive pole and negative side place aluminium foil and Copper Foil as collector, draw lug, fix battery by the way of thermoplastic envelope and finish
And realization and the isolation of air.
Under 0.2C multiplying powers, the charge-discharge performance of the battery is tested, as shown in Figure 10, it can be found that its first charge-discharge
Can be very poor, then can not normally discharge and recharge.Figure 11 gives its interface impedance spectrum, it can be found that impedance is larger, boundary at room temperature
Face impedance about 48m Ω m2.One of the reason for this is also its charge-discharge performance difference.
Comparative example two
With LiCoO of the prior art2As positive pole, using the LATP of same embodiment two as solid electrolyte, by with
Lower technique prepares lithium battery：
(1) the LATP solid electrolyte flakes that thickness is 200 μm are taken, size is 2cm × 2cm, and conductivity at room temperature reaches
To 8 × 10-4S/cm；
(2) by LiCoO2With LATP solid electrolytes according to 75:25 ratio mixing, and add first two material mass it
The electrically conductive graphite of the 2% of sum prepares anode composite；The anode composite of 3mg or so is taken, the ethyl cellulose and pine tar of 1.4mg is added
The solvent that alcohol etc. has been configured prepares slurry, is uniformly coated on solid electrolyte flake slurry using silk-screen printing, 65 degree
Drying 24h；
(3) after drying, the electrolyte sheet of anode composite is coated with Ar gas atmosphere, 400 DEG C process 2h；
(4) Li-In alloys are affixed on the opposite side of solid electrolyte after being disposed in glove box, and respectively in positive pole
Aluminium foil and Copper Foil are placed as collector with negative side, lug is drawn, and battery is fixed finishing and real by the way of thermoplastic envelope
Now with the isolation of air.
Under 0.2C multiplying powers, the cycle performance and coulombic efficiency of the battery are tested, as shown in figure 12.Although LiCoO2As
During positive pole, circulation 15 discharge capacities up to 100mAh/g or so, but more than 20 times after capacity attenuation clearly, approach
80mAh/g.Figure 13 gives the interface impedance spectrum of the battery, it is found that impedance is compared compared with battery in embodiment one, be increased
2.5 times, interface impedance about 20m Ω m at room temperature2, this be also its charge-discharge performance difference the reason for one of.
Claims (9)
1. a kind of solid lithium battery, including positive pole, negative pole and the solid electrolyte between positive pole and negative pole, its feature
It is that the main component in the solid electrolyte is LiM2(PO4)3Based compound, the main component in the positive pole is Li3V2
(PO4)3Based compound and LiM2(PO4)3One kind or several in based compound, wherein M=Ge, Ti, Hf, Al, Si, V, Sc or Zr
Kind；The Li3V2(PO4)3Based compound and LiM2(PO4)3Based compound is NASICON structures.
2. solid lithium battery according to claim 1, it is characterised in that the LiM2(PO4)3Based compound is Li1+ xAlxTi2-x(PO4)3Or Li1+xAlxGe2-x(PO4)3, wherein 0≤x≤1.
3. solid lithium battery according to claim 1 and 2, it is characterised in that the LiM2(PO4)3Based compound is Si
Or the compound of B or Fe doping.
4. solid lithium battery according to claim 1 and 2, it is characterised in that the Li3V2(PO4)3Based compound is C
The Li of cladding3V2(PO4)3Base active material.
5. solid lithium battery according to claim 1, it is characterised in that the positive pole also includes conductive agent.
6. solid lithium battery according to claim 5, it is characterised in that the conductive agent is conductive black, conductive stone
One or more in ink, Graphene, carbon fiber, CNT or fullerene.
7. solid lithium battery according to claim 1, it is characterised in that the Li in the positive pole3V2(PO4)3Base chemical combination
Thing and LiM2(PO4)3The mass ratio of based compound is 9:(1~9).
8. the solid lithium battery according to claim 5 or 6, it is characterised in that the content of the conductive agent is Li3V2
(PO4)3Based compound and LiM2(PO4)3The 1~10% of based compound quality sum.
9. solid lithium battery according to claim 1, it is characterised in that the solid electrolyte be thickness be 50~
500 microns of laminated structure.
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| CN107546380A (en) * | 2017-08-22 | 2018-01-05 | 电子科技大学 | A kind of lithium ion battery composite cathode material and preparation method thereof |
| CN108987687A (en) * | 2018-06-22 | 2018-12-11 | 中南大学 | A kind of low-temperature lithium ion battery graphite cathode material and preparation method thereof |
| WO2019069179A1 (en) * | 2017-10-02 | 2019-04-11 | International Business Machines Corporation | High-performance thin-film battery with an interfacial layer |
| CN109935897A (en) * | 2017-12-19 | 2019-06-25 | 成都英诺科技咨询有限公司 | Solid electrolyte and its lithium battery electric core, lithium battery |
| DE102018102387B3 (en) | 2018-02-02 | 2019-06-27 | Schott Ag | Glass-ceramic with ion-conducting residual glass phase and process for its preparation |
| CN110661033A (en) * | 2018-06-28 | 2020-01-07 | 宁德时代新能源科技股份有限公司 | Ion exchange material, preparation method thereof, electrolyte film and secondary battery |
| CN111699583A (en) * | 2018-03-29 | 2020-09-22 | Tdk株式会社 | All-solid-state secondary battery |
| CN111987348A (en) * | 2020-08-27 | 2020-11-24 | 电子科技大学 | Preparation method of NASICON type solid-state battery |
| WO2020258803A1 (en) * | 2019-06-26 | 2020-12-30 | 上海空间电源研究所 | Lithium-ion solid electrolyte and preparation method therefor |
| CN112968254A (en) * | 2021-01-29 | 2021-06-15 | 东莞维科电池有限公司 | Diaphragm for lithium ion battery, preparation method of diaphragm and lithium ion battery |
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