A kind of solid lithium battery with gradient-structure and preparation method thereof
Technical field
The present invention relates to a kind of solid lithium battery with gradient-structure and preparation method thereof, belong to solid state battery field.
Background technology
Under the background of the dual trend of energy crisis and environmental protection, development new-energy automobile, as motor vehicle (EV), motor vehicle driven by mixed power (HEV) and plug-in hybrid electric vehicle (PHEV), has become active demand.And battery is as the energy storage device of new-energy automobile, become one of core key technology of new-energy automobile.
Than liquid state electrolyte battery, all-solid-state battery improving energy content of battery density, widen working temperature interval, also have larger development space aspect increasing the service life.Since entering 21 century, diversification has become the important development direction in secondary cell field, and when widening battery applications field, people also more and more pay attention to battery to carry out personalized design, to improve performance and the thermal adaptability of battery.
Be different from liquid battery, the electrolyte of all-solid-state battery and electrode compatibility are poor, and the large multiplying power discharging property of battery is poor.Electrolyte is electrochemical reaction avtive spot place to the wettability of electrode, be electronics and the ion unimpeded important leverage of passage of " meeting ", and the Low ESR at electrode interface place is the key that determines battery performance.For solid-liquid electrode interface, there is not much problems, but for solid/liquid/solid interface, because solid electrolyte does not have the wettability of liquid electrolyte, the solid state battery made from solid electrolyte, generally also than body impedance large one more than the order of magnitude of its interface impedance.Therefore, from the structural design of battery, take into full account electrode and become very important with electrolytical contact.
On the other hand, if cell electrode layer is comprised of uniform electrolyte and electrode material in three-dimensional, so in battery discharge procedure, lithium ion in electrolyte in active positive electrode material layer is inhaled in electrode active material particles fast, and in electrode active material layers, the reduction of electrolytical lithium concentration is spread and supplemented from dielectric substrate by lithium ion.Meanwhile, the electronics of collector electrode conducts by electric conducting material, thereby promotes electrode reaction.And lithium ion is diffused into electrode material layer speed from dielectric substrate is slowly with respect to the conduction of electronics.Under discharging and recharging at a high speed, the lithium ion of positive electrode material layer is tending towards exhausting, and along with the direction to collector electrode, this trend increases.The speed of electrode reaction is unable to catch up with in the diffusion of lithium ion, causes occurring larger overvoltage, and battery cannot provide theoretical charge/discharge capacity, and the fast charging and discharging performance of battery declines.
Summary of the invention
For cell electrode layer in prior art, be mainly that electrolyte and electrode material concentration are uniformly distributed, existence under large current rate in charge or discharge process Li ion easily exhaust, the defect that causes the battery performance reduction of charge or discharge capacity, and there is the solid lithium battery of kind electrode layer, electrode contacts easy variation with electrolytical, interface impedance is very large, battery cannot high rate charge-discharge, the object of the invention is to be to provide a kind of stable at high rate charge-discharge, the solid lithium battery with gradient-structure that can normally work under large current rate.
Another object of the present invention is to be to provide a kind of process simple, has the method for the solid lithium battery of gradient-structure described in low-cost preparation.
The invention provides a kind of solid lithium battery with gradient-structure, this solid lithium battery, is comprised of the negative pole that has positive pole, solid electrolyte layer and the metal negative pole of gradient-structure layer or have a gradient-structure layer; Described gradient-structure layer is component concentration in gradient continually varying electrode layer, component granularity continually varying electrode layer or component molecular weight continually varying electrode layer in gradient in gradient.
Described gradient is that the size of exponential quantity is continuous variation, can be the ascending or descending continuous variation of numerical value.
Described component concentration in gradient continually varying electrode layer is preferably the mass percent concentration of electrode material in electrode layer and forms the electrode layer progressively reducing to dielectric substrate direction from collector electrode.
The described component granularity granularity that continually varying electrode layer is preferably electrode active material in gradient forms the electrode layer progressively increasing to dielectric substrate direction from collector electrode in electrode layer.
The described component molecular weight molecular weight that continually varying electrode layer is preferably polyelectrolyte in gradient forms the electrode layer progressively increasing to dielectric substrate direction from collector electrode in electrode layer.
Described component concentration in gradient continually varying electrode layer at least comprises the rete of two variable concentrations components; Be preferably the rete that at least comprises three variable concentrations components; Most preferably be the rete that at least comprises five variable concentrations components.
Described component granularity in gradient continually varying electrode layer at least comprises the rete of two different grain size components; Be preferably the rete that at least comprises three different grain size components; Most preferably be the rete that at least comprises five different grain size components.
Described component molecular weight in gradient continually varying electrode layer at least comprises the rete of two different molecular weight components; Be preferably the rete that at least comprises three different molecular weight components; Most preferably be the rete that at least comprises five different molecular weight components.
The thickness of described rete is 1~100 μ m.
Described dielectric substrate thickness is 1~30 μ m.
Positive electrode active materials in described electrode active material comprises LiCoO
2li-Co composite oxides family, LiNiO
2li-Ni composite oxides family, LiMn
2o
4li-Mn composite oxides family, and LiFePO
4li-Fe composite oxides family, or as Li (NiCoMn) O
2li-Ni-Mn-Co-O composite oxides, LiMn
0.7fe
0.3pO
4iron manganese phosphate for lithium compound etc.; Negative active core-shell material comprises Li
4ti
5o
12, graphite or lithium metal etc.
Described solid electrolyte layer comprises inorganic electrolyte material layer or polymer electrolyte, and inorganic electrolyte material comprises Ca-Ti ore type, LISICON type, NASICON type, stratiform Li
3n class, LiPON class, oxide glass state and chalcogenide glass state electrolyte, polymer electrolyte comprises polyoxyethylene base electrolyte, polyoxyethylene deriv base electrolyte and polysiloxanes base electrolyte etc.
Solid lithium battery of the present invention can be assembled into the battery of internal series-connection, internal parallel or both mixing, by modes such as lamination, volume to volume, prepares difform solid lithium battery unit.
The present invention also provides a kind of method of preparing the described solid lithium battery with gradient-structure, comprises the following steps:
A) by different quality than electrode material be mixed with electrolyte many groups anode sizing agent that electrode material mass percentage content is different; Or varigrained electrode active material is made into electrode material with auxiliary material respectively, then is mixed with electrolyte many groups anode sizing agent that electrode active material granularity is different; Or the polyelectrolyte of different molecular weight and electrode material are mixed with to the different many groups positive electrode of polyelectrolyte molecular weight; By the many groups anode sizing agent preparing by the gradient of electrode material mass percent concentration, or the gradient of electrode active material granularity, or the gradient of polyelectrolyte molecular weight is coated in collector electrode surface successively, obtains having the anodal layer of gradient-structure;
B) configuration electrolyte slurry, is coated in a) the anodal layer surface with gradient-structure of gained by described electrolyte slurry, obtains dielectric substrate;
C) directly at b) described dielectric substrate surface adhesion metal electrode; Or according to the many groups of the method preparation cathode sizes of a) preparing anode sizing agent, by described many group cathode sizes by electrode material mass percent concentration and a) contrary concentration gradient or by electrode active material granularity and a) contrary granular gradient or by polyelectrolyte molecular weight and a) contrary molecular weight gradient be coated in successively b) dielectric substrate on, adhesion collector electrode again, must have the solid lithium battery of gradient-structure.
Described auxiliary material comprises electric conducting material and bonding agent.
Described coating can be the methods such as ink-jet, blade coating or silk screen printing.
The anodal layer of the inventive method and the preparation of dielectric substrate, can also use the method preparations such as magnetron sputtering, vapour deposition.
Beneficial effect of the present invention: first passage of the present invention is designed to have the gradient-structure layer that component concentration in gradient changes continuously or component granularity changes in gradient or component molecular weight changes in gradient by the electrode layer of electrode in solid lithium battery, effectively improve the diffusion rate of lithium ion in electrode layer, the battery of assembling does not have obvious solid electrolyte and electrode interface simultaneously, can realize the Maximum Contact of electrode material and solid electrolyte; The solid lithium battery with this gradient-structure layer can be realized and discharging and recharging under large multiplying power, under large current rate, also can normally work; In addition the individual layer battery that, has a this gradient-structure layer can be prepared the battery of lamination or convoluted various shape.
Accompanying drawing explanation
[Fig. 1] is the solid lithium battery schematic diagram of the embodiment of the present invention 1 preparation.
The solid lithium battery that [Fig. 2] is the embodiment of the present invention 1 preparation with and the solid lithium battery prepared of comparative example at the charging and discharging curve of room temperature 1C multiplying power.
[Fig. 3] is the solid lithium battery schematic diagram of the embodiment of the present invention 2 preparations.
[Fig. 4] is the solid lithium battery schematic diagram of the embodiment of the present invention 3 preparations.
[Fig. 5] is the solid lithium battery schematic diagram of the embodiment of the present invention 4 preparations.
[Fig. 6] is the stacked solid lithium battery schematic diagram of cylindrical interior string: 61 for cell integrated; 62 is negative pole exit; 63 is negative pole coating; 64 is anodal coating; 65 is solid electrolyte; 66 is collector electrode; 67 is insulating barrier; 68 is anodal exit; 69 is battery case.
[Fig. 7] is the stacked solid lithium battery schematic diagram of square interior string: 71 is anodal exit; 72 is shell; 73 is solid electrolyte; 74 is collector electrode interlayer dielectic; 75 is collector electrode and exit insulating material; 76 is negative pole coating; 77 is anodal coating; 78 is negative pole exit.
Embodiment
The invention is further illustrated by the following examples, and the present invention is not limited only to described embodiment.
Embodiment 1
(a) change the amount of electrode material and the solid electrolyte will be added to form electrode layer, making the mass fraction of electrode material is 10%, 50%, 100%, prepares anode sizing agent.Wherein electrode material is LiFePO
4, polyvinylidene fluoride and conduction charcoal (mass ratio 8:1:1) mixture, electrolyte is the mixture of polysiloxanes and lithium salts (mass ratio 8:2), slurry at room temperature has the viscosity of 3cP;
(b) with described multiple anode sizing agent, apply collector electrode, make positive electrode concentration gradient along with reducing to anodal layer surface order from electrode active material layers collector electrode, thus the different anode thin film layer of stacked a plurality of solid concentration; Each anode thin film layer thickness is about 50 μ m left and right;
(c) configuration electrolyte slurry, is coated on anodal established thin layer, and thickness is about 15 μ m left and right;
(d) collector electrode of containing metal lithium is pressed on the electrolytic thin-membrane of formation, finally with battery case, encapsulates.
Fig. 1 has represented to have the solid lithium battery of concentration of component gradient.
Comparative example 1
Identical in experiment condition and embodiment 1, just electrode material and solid electrolyte are mixed to be coated on collector electrode and make electrode layer, do not form the concentration gradient of electrode material.
The solid lithium battery that embodiment 1 and comparative example 1 make is put into insulating box, and temperature remains on 25 ℃, uses charge and discharge device to carry out the test of 1C multiplying power discharging property.
The solid lithium battery discharge rate of embodiment 1 is 73%, and comparative example 1 solid lithium battery discharge rate is 66%, and the former has higher discharge platform, thereby the former battery is more superior.Voltage and capacity relationship are as shown in Figure 2.
Embodiment 2
(a) mix a certain amount of spinel structure LiMn
2o
4for positive electrode active materials, a certain amount of acetylene black is as electric conducting material, a certain amount of polyvinylidene fluoride is bonding agent, three's mass ratio is 9:5:5, a certain amount of polysiloxanes and lithium salts, both ratios are 8:2, make electrolyte components and the constituent mass ratio of electrode material maintain 7:3, change LiMn
2o
4granularity (0.1 μ m, 0.3 μ m, 0.6 μ m), thereby prepare the multiple anode sizing agent of different activities material particle size;
(b) with described multiple anode sizing agent, apply collector electrode, make positive electrode active materials granularity along with increasing to anodal layer surface order from electrode active material layers collector electrode, each anode thin film layer thickness is about 50 μ m left and right;
(c) configuration electrolyte slurry, siloxanes and lithium salts, both ratios are 8:2, are coated on anodal established thin layer, thickness is about 15 μ m left and right;
(d) mixing a certain amount of graphite is negative active core-shell material, a certain amount of acetylene black is as electric conducting material, a certain amount of polyvinylidene fluoride is bonding agent, and three's mass ratio is 9:5:5, a certain amount of polysiloxanes and lithium salts, both ratios are 8:2, make electrolyte components and the constituent mass ratio of electrode material maintain 7:3, change granularity (0.1 μ m, the 0.3 μ m of graphite, 0.6 μ m), thus prepare the multiple cathode size of different activities material particle size;
(e) with described multiple cathode size, apply collector electrode, make negative electrode active material material granularity along with the surface of dielectric substrate reduces to collector electrode, thus the negative film layer of stacked a plurality of different activities material granularities.
Fig. 2 has represented to have the solid lithium battery of electrode active material granularity.
Embodiment 3
(a) mix a certain amount of LiCoO
2for positive electrode active materials, a certain amount of acetylene black is as electric conducting material, a certain amount of polyvinylidene fluoride is bonding agent, and three's mass ratio is 9:5:5, a certain amount of polyoxyethylene and lithium salts, both ratios are 8:2, make electrolyte components and the constituent mass ratio of electrode material maintain 7:3, the polyoxyethylated molecular weight (8000,400000 of change, 4000000), thus prepare the different multiple anode sizing agent of molecular weight of electrolytic polymer;
(b) with described multiple anode sizing agent, apply collector electrode, make polyoxyethylene molecular weight along with increasing to anodal layer surface order from collector electrode, each anode thin film layer thickness is about 50 μ m left and right;
(c) configuration electrolyte slurry, polyoxyethylene (molecular weight 4000000) and lithium salts, both ratios are 8:2, are coated on anodal established thin layer, thickness is about 15 μ m left and right.
(d) mixing a certain amount of graphite is negative active core-shell material, a certain amount of acetylene black is as electric conducting material, a certain amount of polyvinylidene fluoride is bonding agent, and three's mass ratio is 9:5:5, a certain amount of polyoxyethylene and lithium salts, both ratios are 8:2, make electrolyte components and the constituent mass ratio of electrode material maintain 7:3, change polyoxyethylated molecular weight (8000,400000,4000000), thus prepare the different multiple cathode size of molecular weight of electrolytic polymer;
(e) with described multiple cathode size, apply collector electrode, make polyoxyethylated molecular weight along with the surface of dielectric substrate reduces to collector electrode, thus the negative film layer of stacked a plurality of different activities material granularities.
Fig. 3 has represented to have the solid lithium battery that electrolytic polymer molecular weight gradient changes.
Embodiment 4
(a) mix a certain amount of LiCoO
2for positive electrode active materials, a certain amount of acetylene black is as electric conducting material, a certain amount of polyvinylidene fluoride is bonding agent, three's mass ratio is 9:5:5, and a certain amount of polysiloxanes and lithium salts make electrolyte components and the constituent mass ratio of electrode material maintain 7:3, change the ratio (8:2 of polysiloxanes and lithium salts, 7:3,6:4), thus prepare the multiple anode sizing agent that electrolyte lithium salinity is different;
(b) with described multiple anode sizing agent, apply collector electrode, the content of lithium salts reduces to anodal layer surface order from collector electrode, and each anode thin film layer thickness is about 50 μ m left and right;
(c) configuration electrolyte slurry, polysiloxanes and lithium salts, both ratios are 8:2, are coated on anodal established thin layer, thickness is about 15 μ m left and right;
(d) mixing a certain amount of graphite is negative active core-shell material, a certain amount of acetylene black is as electric conducting material, a certain amount of polyvinylidene fluoride is bonding agent, three's mass ratio is 9:5:5, and a certain amount of polysiloxanes and lithium salts make electrolyte components and the constituent mass ratio of electrode material maintain 7:3, change the ratio (8:2 of polysiloxanes and lithium salts, 7:3,6:4), thus prepare the multiple cathode size that electrolyte lithium salinity is different;
(e) with described multiple cathode size, apply collector electrode, make lithium salt along with the surface of dielectric substrate increases to collector electrode, thus the negative film layer of stacked a plurality of different lithium salinity.
Fig. 4 has represented to have the solid lithium battery of electrolyte concentration graded.
Embodiment 5
From inner electrical connection angle, according to the formed solid lithium battery of embodiment 1~4, can be designed to internal series-connection battery unit or internal parallel battery unit.Internal series-connection battery has higher voltage as simple battery, and has excellent capacity and output characteristic.According to the solid lithium battery of embodiment, preferably manufacture internal series-connection battery.Sheet cell in stacked embodiment 1~4, in both positive and negative polarity thin layer, there is dielectric substrate to separate, then encapsulate whole lamination and with the stacking material sealing that forms battery case, only make positive pole and negative wire be exposed to outside, thereby solid lithium battery unit is provided.