CN111370751A - Solid-state battery, preparation method thereof and electric automobile - Google Patents
Solid-state battery, preparation method thereof and electric automobileDownload PDFInfo
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Abstract
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a solid-state battery, a preparation method thereof and an electric automobile.
Background
The inorganic all-solid-state lithium battery is a lithium ion battery which is assembled by utilizing a solid electrolyte and a positive electrode and a negative electrode together, and because the inorganic all-solid-state lithium battery does not use an organic electrolyte, the safety is greatly improved, and higher energy density and longer cycle life are expected. The battery is composed of powdered solid electrolyte, composite negative electrode and composite positive electrode, or is composed of Li in alloy negative electrode and solid battery. The quality of the solid-state battery assembly process directly influences the quality of the contact among the particles, and further influences the overall performance of the battery.
The assembly of the original solid-state battery has the following disadvantages: 1. the electrode material, especially the anode material and the electrolyte powder are mixed and pressurized for assembly, so that larger particle gaps exist, the compaction density is lower, and the volume energy density is reduced. 2. The contact problem among particles is serious, the grain boundary resistance is increased, and the final performance of the battery is influenced. 3. The assembly of the positive plate and the electrolyte is formed by two pressing, and a serious interface problem often exists between the positive plate and the electrolyte, so that the internal resistance of the battery is increased. 4. If the lithium cathode is directly used, the problem of lithium dendrite short circuit is serious, and if lithium metal is not suitable for the cathode, the energy density is reduced, so that the electrolyte or the lithium cathode must be modified, and the process difficulty and the cost of the whole battery assembly are increased.
Disclosure of Invention
In view of at least one of the above problems, the present invention provides a solid-state battery including a positive electrode layer, a solid-state electrolyte layer on a surface of the positive electrode layer, and a negative electrode current collector on a surface of the solid-state electrolyte layer; the positive electrode layer comprises a positive electrode current collector and a positive electrode active material layer positioned on the surface of the positive electrode current collector, the positive electrode active material layer comprises positive electrode active particles and a first solid electrolyte, and the first solid electrolyte is coated on the surfaces of the positive electrode active particles and/or filled among the positive electrode active particles in a state of complete melting and then quenching; the solid electrolyte layer includes a second solid electrolyte bonded between the positive electrode layer and the negative electrode current collector in a completely molten state and then quenched, respectively; the density of the solid-state battery is 96-100%.
Preferably, the electrochemical impedance of the solid-state battery is 1 to 100 Ω.
Preferably, the volume energy density of the solid-state battery is 1000-1500 Wh/L.
Preferably, the first solid electrolyte and the second solid electrolyte are each independently selected from one or more of a sulfur-based solid electrolyte, an anti-perovskite type solid electrolyte, a NASICON type solid electrolyte and a perovskite type solid electrolyte.
Preferably, the positive electrode layer and/or the solid electrolyte layer further comprises a flux, and the flux is LiI, LiBr, LiF, Li2O，P2Se5，P2O5ZnO and Li3PO4One or more of (a).
A second object of the present invention is to provide a method for manufacturing a solid-state battery, the method comprising the steps of:
s1, providing a positive electrode layer, and heating the positive electrode layer to completely melt the first solid electrolyte particles in the positive electrode layer; the positive electrode layer comprises a positive electrode current collector and a positive electrode active material layer positioned on the surface of the positive electrode current collector, and the positive electrode active material layer comprises positive electrode active particles and first solid electrolyte particles;
s2, providing a composite layer, and heating the composite layer to completely melt the second solid electrolyte particles in the composite layer; the composite layer comprises a negative current collector and a solid electrolyte layer positioned on the surface of the negative current collector, wherein the solid electrolyte layer comprises second solid electrolyte particles;
and S3, laminating the positive electrode layer melted in the step S1 and the composite layer melted in the step S2, controlling the laminating time of the positive electrode layer and the composite layer to be 1-300S, and then quenching to obtain the solid-state battery.
Preferably, the preparation method of the positive electrode layer comprises the steps of uniformly mixing the positive electrode active particles and the first solid electrolyte particles, and then carrying out hot pressing on the mixture and a positive electrode current collector to form a positive electrode sheet; the hot pressing temperature is 150-300 ℃, the hot pressing time is 5min-2h, and the hot pressing pressure is 10-1000 MPa.
Preferably, the preparation method of the composite layer includes the steps of coating second solid electrolyte slurry obtained by dissolving second solid electrolyte particles in a solvent on the surface of the negative current collector, and drying to obtain the composite layer; the solvent is one or more of NMP, ethanol, acetone, benzene and toluene.
Preferably, in the step S1, the heating temperature is 600-850 ℃, and the heating time is 10min-2 h; the heating temperature in the step S2 is 600-850 ℃, and the heating time is 20min-12 h.
Preferably, the quenching rate is 5 ℃/s-100 ℃/s.
Preferably, the quenching mode is air quenching.
A third object of the present invention is to provide a solid-state battery produced by the method described above.
A fourth object of the invention is to provide an electric vehicle including the solid-state battery described above.
In the prior art, the solid electrolyte material exists in the positive electrode layer and/or the solid electrolyte layer in a granular form, and compared with the prior art, the positive electrode material has the following beneficial effects: in the application, the first solid electrolyte is coated on the surface of the positive active particles and/or filled between the positive active particles in a state of complete melting and then quenching, and the second solid electrolyte is clamped between the positive electrode layer and the negative current collector in a state of complete melting and then quenching, so that the positive active particles and the positive active particles, the positive active particles and the first solid electrolyte, the positive layer and the solid electrolyte layer, and the second solid electrolyte are in good contact without obvious gaps, the electrochemical impedance of the solid battery is obviously reduced, and the compactness is as high as 96-100%; the solid-state battery has high compactness, so that the solid-state battery directly serves as a negative current collector without a negative active substance during assembly, the weight of the whole solid-state battery is reduced, the volume energy density of the solid-state battery is improved, the short circuit problem caused by the growth of lithium dendrites can be greatly inhibited due to the high compactness of the solid-state battery, and the charge and discharge performance and the cycle performance of the solid-state battery are obviously improved.
The above and other features and advantages of the present invention will be further explained from the following detailed description.
Drawings
FIG. 1 is a scanning electron microscope photograph of a solid-state battery prepared in example 1; the magnification is 1000 times;
FIG. 2 is a scanning electron microscope photograph of a solid-state battery prepared in comparative example 3 at a magnification of 158 times;
FIG. 3 is a scanning electron microscope photograph of a solid-state battery prepared in comparative example 3 at a magnification of 500;
FIG. 4 is a scanning electron microscope photograph of a solid-state battery prepared in comparative example 3 at a magnification of 1000;
FIG. 5 is a scanning electron microscope photograph of the solid-state battery prepared in comparative example 2 at a magnification of 500;
① positive electrode layer, ② solid electrolyte layer, ③ negative electrode current collector.
Detailed Description
In the existing solid-state battery, solid electrolyte particles and positive electrode active particles are usually dissolved in a solvent to form slurry, the slurry is coated on a positive electrode current collector to form a positive electrode active layer, electrolyte slurry is coated on the surface of the positive electrode active layer, and the solid-state battery is assembled with a negative electrode layer after drying.
In view of the above problems of the conventional solid-state battery, the present invention provides a solid-state battery, which includes a solid-state electrolyte layer located on the surface of an anode layer and a cathode current collector located on the surface of the solid-state electrolyte layer; the positive electrode layer comprises a positive electrode current collector and a positive electrode active material layer positioned on the surface of the positive electrode current collector, the positive electrode active material layer comprises positive electrode active particles and a first solid electrolyte, and the first solid electrolyte is coated on the surfaces of the positive electrode active particles and/or filled among the positive electrode active particles in a state of complete melting and then quenching; the solid electrolyte layer comprises a second solid electrolyte which is clamped between the positive electrode layer and the negative electrode current collector in a state of complete melting and then quenching; the density of the solid-state battery is 96-100%.
In the present application, the state after completely melting and then quenching is formed by melting the first solid electrolyte and the second solid electrolyte by heating (referred to as a melt) and then rapidly cooling, which is to avoid crystallization; when the solid electrolyte is melted at high temperature, the solid electrolyte melt is connected together in a large area, gaps between original solid electrolyte particles and original solid electrolyte particles do not exist, and the solid electrolyte can be kept in an amorphous state when melted at high temperature due to rapid cooling, so that the compactness is obviously improved. The complete melting of the solid electrolyte means that the whole solid electrolyte particle is completely melted, that is, the solid electrolyte particle is melted not only at the interface but also inside the particle, at this time, the original edge shape of the solid electrolyte particle is not existed, all the solid electrolytes are connected together in a large area after being melted, and no obvious particle can be seen after being rapidly cooled.
The positive electrode layer comprises positive electrode active particles and a first solid electrolyte, the positive electrode active particles are not melted at the interface or in the particles, the positive electrode active particles still keep the inherent crystal structure and the microstructure, so that the lithium removal and lithium insertion performance of the positive electrode active particles is not influenced, the first solid electrolyte is melted, the positive electrode active particles are not melted, the melted first solid electrolyte has good fluidity and can be filled between the positive electrode active particles, after the melted first solid electrolyte is rapidly cooled, at least part of the first solid electrolyte is coated on the surface of the positive electrode active particles and/or at least part of the first solid electrolyte is filled between the positive electrode active particles, and therefore, no obvious gap exists between the positive electrode active particles and the positive electrode active particles.
The solid electrolyte layer comprises a second solid electrolyte which can be completely melted after heat treatment, the melted electrolytes are connected together in a large area, after the second solid electrolyte is cooled, the appearance of the whole solid electrolyte layer is as smooth glass, no obvious particles exist, no obvious pores exist, the strength and the hardness are obviously improved, and the short circuit of the battery caused by the fact that lithium dendrites penetrate through the solid electrolyte layer can be fundamentally inhibited. .
It should be noted that, ideally, the technical solution of the present application is to completely melt all the solid electrolyte, and no obvious particles exist in the solid electrolyte layer, but in practical cases, there may be a very small part of the second solid electrolyte in the form of particles which is not completely melted, but the content thereof is far less than 1%, and the situation is also within the protection scope of the present application.
In the application, the first solid electrolyte and the second solid electrolyte exist in the positive electrode layer and the solid electrolyte layer respectively in a state of complete melting and quenching immediately, so that no obvious gap exists between positive electrode active particles and positive electrode active particles, between the positive electrode layer and the solid electrolyte layer, between the second solid electrolyte and between the solid electrolyte layer and a negative electrode current collector, the electrochemical impedance of the solid battery is low, and the density of the solid battery is as high as 96-100%. The highly dense solid-state battery can fundamentally suppress the short-circuit problem caused by the growth of lithium dendrites.
In the prior art, in order to improve the compactness of a solid-state battery, the temperature at the interfaces of positive active particles, solid electrolyte particles and negative active particles is also heated by a rapid interface heating mode to a degree that the interfaces are melted, so that the interfaces between the solid electrolyte particles and the positive active particles, between the solid electrolyte particles and between the solid electrolyte particles and the negative active particles are locally melted, but the rapid interface heating only melts the interfaces of the solid electrolyte particles without melting the inside of the particles, and compared with the complete melting of the solid electrolyte particles, the interface melting cannot achieve high compactness, has high electrochemical impedance and is easy to grow lithium dendrites to cause short circuit.
In the present application, the positive active material layer further includes a conductive agent, the conductive agent includes a carbon material, and may be non-graphitized carbon, graphite, or one or more of carbon obtained by high-temperature oxidation of a polyacetylene-based polymer material, pyrolytic carbon, coke, an organic polymer sinter, and activated carbon, which is common general knowledge of those skilled in the art and is not described herein again. The first solid electrolyte is coated on the surface of the conductive agent and/or filled in the gap between the conductive agent and/or the gap between the conductive agent and the positive electrode active particle in a state of being completely melted and then quenched.
The density of the solid-state battery is defined as the ratio of the actual density to the theoretical density of the solid-state battery, and the calculation formula of the actual density is as follows:
when calculating the density, the density is not included in the positive electrode current collector and the negative electrode current collector, that is, only the positive electrode active material layer and the solid electrolyte layer are considered when calculating the density.
The theoretical density is calculated by the formula:
where ρ isFruit of Chinese wolfberryActual density of the solid-state battery, ρTheory of thingsIs the theoretical density, ρ, of a solid-state batteryIs justTheoretical density of positive electrode active material layer, pFixing deviceIs the theoretical density, p, of the second solid electrolyte1The theoretical density of the positive electrode active particles can be found in the literature, p2The theoretical density of the first solid electrolyte can be examined in the literatureTo, ρ3M, which is the theoretical density of the conductive agent in the positive electrode active material layer, can be found in the literatureIs justMass m of the positive electrode active material layerFixing deviceQuality of the solid electrolyte layer, DIs justThickness of the positive electrode active material layer, DFixing deviceIs the thickness of the solid electrolyte layer, S is the area of the solid battery, specifically the spreading area of the positive electrode active material layer or the spreading area of the solid electrolyte layer, w1Is the mass fraction, w, of the positive electrode active particles in the positive electrode active material layer2Is the mass fraction, w, of the first solid electrolyte in the positive electrode active material layer3Is the mass fraction of the conductive agent in the positive electrode active material layer.
At present, lithium metal has higher theoretical capacity and is expected to be widely applied compared with graphite, but lithium metal is easy to react with an electrolyte, so that the solid electrolyte is adopted to replace the traditional electrolyte, and the solid electrolyte using a lithium metal negative electrode still has some inherent defects. Currently, the biggest impediment to the application of lithium metal negative electrodes to batteries is the cycling stability and safety of lithium metal. In the circulation process of the lithium battery, lithium ions are repeatedly deposited and separated on the surface of the lithium metal, so that the surface flatness of the lithium metal is easily reduced, the current density distribution is uneven, lithium dendrites are further formed, and potential safety hazards are brought. Resulting in rapid degradation of the cycle performance of the lithium battery. The cycling performance of the battery is further degraded if the deposited lithium detaches from the lithium metal surface to form "dead lithium". In addition, since lithium metal is very active in chemical properties, if lithium metal is directly used as a negative electrode, environmental temperature and humidity must be strictly controlled during the battery manufacturing process, which undoubtedly increases the manufacturing cost.
If the lithium metal negative electrode is not directly used during the manufacturing of the lithium battery, lithium ions which are extracted from the positive electrode can be reversibly deposited and extracted on the negative electrode current collector during the working of the battery, the manufacturing process of the battery does not need strict environmental control any more, the manufacturing difficulty can be obviously reduced, and the manufacturing cost can be reduced. However, the conventional solid-state battery has low compactness, and gaps between solid electrolyte particles and positive active particles, gaps between solid electrolyte particles and solid electrolyte particles, and gaps between solid electrolyte particles and negative active particles are large, so that electrochemical impedance is large, contact is poor in a circulation process, and dead lithium continuously occurs, so that capacity is continuously and rapidly attenuated, and therefore, the conventional solid-state battery cannot directly remove lithium metal, and a negative electrode loaded with a certain amount of lithium metal is required to supplement loss generated in the circulation process.
According to the solid-state battery provided by the application, because the first solid-state electrolyte and the second solid-state electrolyte exist in a state of being completely melted and then quenched, the positive electrode layer and the solid-state electrolyte layer are in good contact, the electrochemical impedance is lower, specifically, the electrochemical impedance of the solid-state battery is 1-100 omega, the negative electrode layer can be directly a blank current collector without an active material layer, lithium ions coming out of the positive electrode can be reversibly deposited and come out on the negative electrode current collector when the battery works, the weight of the whole solid-state battery is reduced due to the fact that the negative electrode active material is not adopted, the volume energy density of the solid-state battery is obviously improved, and specifically, the volume energy density of the solid-state battery is 1000 + 1500 Wh/L.
The first solid electrolyte and the second solid electrolyte are not particularly limited in kind, and may be melted at a high temperature and assembled into a compact solid battery after being rapidly cooled, and preferably, the first solid electrolyte and the second solid electrolyte are each independently selected from one or more of a chalcogenide solid electrolyte, an anti-perovskite solid electrolyte, a NASICON solid electrolyte, and a perovskite solid electrolyte.
The first solid electrolyte and the second solid electrolyte may be the same or different, and the present application is not particularly limited.
Wherein the sulfur-based solid electrolyte is Li in a glassy state2S-P2S5Crystalline form of Lix＇My＇PSz＇Or Li in the form of glass-ceramics2S-P2S5Wherein M is one or more of Si, Ge and Sn, x '+ 4 y' + 5 = 2z ', 0 ≤ y' is ≤ 1; wherein Li2S-P2S5Refers to Li prepared according to a certain proportion2S and P2S5The complex of (a); preferably, in the preparation of Li2S-P2S5When complexed, the Li2S and P2S5The molar ratio of the two is 60: 40-90: 10.
According to the lithium ion battery provided by the invention, the glassy Li2S-P2S5Preferably in the glassy state7P3S11Glassy 70Li2S-30P2S5One or two of them.
In the present invention, Li in a glassy state2S-P2S5Refers to Li2S-P2S5In the glassy state, crystalline state Lix＇My＇PSzRefers to Lix＇My＇PSzCrystalline state of (1), glass-ceramic state of Li2S-P2S5Refers to Li2S-P2S5In the glass-ceramic state, in the glass state, Li7P3S11Refers to Li7P3S11Medium glass state, glassy state 70Li2S-30P2S5Refers to 70Li2S-30P2S5A medium glass state.
The anti-perovskite series comprises Li3OCl、 Li2OHCl、Li3-2x1Bax1ClO、Li3-2x1Bax1Cl0.5I0.5O、Li3-2x1Mgx1ClO、Li3-n1(OH)n1One or more of Hal, wherein 0<x<0.1,0<n1 is less than or equal to 1, and Hal is halogen.
NASICON type solid electrolyte LiM2(PO4)3And dopants thereof, wherein M is Ti, Zr, Ge, Sn or Pb; the doping element In the dopant is selected from one or more of Mg, Ca, Sr, Ba, Sc, Al, Ga, In, Nb, Ta and V;
the chemical formula of the perovskite type solid electrolyte is Ax2By1TiO3、Ax2By1Ta2O6、Ax2By1Nb2O6Or AhMkDn2TiwO3Wherein x is2+3y1=2，h+2k+5n2+4w=6，0＜x2＜2，0＜y1＜2/3，h、k、n2W is both greater than 0; a is at least one of Li and Na elements, B is at least one of La, Ce, Pr, Y, Sc, Nd, Sm, Eu and Gd elements, M is at least one of Sr, Ca, Ba, Ir and Pt elements, and D is at least one of Nb and Ta elements.
Further preferably, the positive electrode layer and/or the solid electrolyte layer further comprise a fluxing agent, the fluxing agent can adjust the viscosity of the first solid electrolyte and the second solid electrolyte in a molten phase so as to ensure that cracks and defects are not easy to occur in the process of rapidly cooling the molten phase, the compactness of the battery is better, the application does not specially limit the type of the fluxing agent, and preferably, the fluxing agent is LiI, LiBr, LiF, Li2O，P2Se5，P2O5ZnO and Li3PO4One or more of (a).
The thickness of the solid electrolyte layer is 100nm to 100 μm, and preferably, the thickness of the solid electrolyte layer is 1 μm to 10 μm. In the prior art, as is well known to those skilled in the art, a solid electrolyte layer needs to transmit lithium ions and also needs a certain mechanical strength to prevent lithium dendrites from puncturing the solid electrolyte layer to cause short circuit, and under the requirement of improving the volumetric energy density of a battery, it is desirable that the thickness of the solid electrolyte layer is as small as possible, but the thickness of the solid electrolyte layer is too small and the mechanical strength is not sufficient, and the existing solid battery assembly process, such as a coating process, is difficult to realize the thickness of the solid electrolyte layer in micron order.
According to the solid-state battery provided by the present application, the positive electrode active particles include almost all of the positive electrode material, specifically, selected from the group consisting of LiCoO2、LiNiO2、LiCox3Ni1-x3O2（0≤x3≤1）、LiCox4Ni1-x4-y2Aly2O2（0≤x3≤1，0≤y2≤1）、LiMn2O4、LiFex4Mny3Mz1O4(M is at least one of Al, Mg, Ga, Cr, Co, Ni, Cu, Zn or Mo, and x is more than or equal to 04≤1，0≤y3≤1，0≤z1≤1，x4+y3+z1=1）、Li1＋x5L1－y4－z2My4Nz2O2(L, M, N represents at least one of Li, Co, Mn, Ni, Fe, Al, Mg, Ga, Ti, Cr, Cu, Zn, Mo, F, I, S and B-0.1-x5≤0.2，0≤y4≤1，0≤z2≤1，0≤y4+z2≤1），LiFePO4、Li3V2(PO4)3、Li3V3(PO4)3、LiVPO4F、Li2CuO2、Li5FeO4And metal sulfides and oxides such as TiS2、V2S3、FeS、FeS2、LiMSx6(M is at least one of transition metal elements such as Ti, Fe, Ni, Cu, Mo and the like, and x is more than or equal to 16≤2.5）、TiO2、Cr3O8、V2O5、MnO2And the like, preferably the particle diameter of the positive electrode particles is in the range of 100nm to 500 μm. In some embodiments, the surface of the positive active particle may further include a coating layer, which is an oxide, a lithium-containing transition metal oxide, or the like, in particular, LiNbO3、LiTaO3、Li4Ti5O12、Al2O3And the like.
The positive current collector can be one or more of aluminum, stainless steel, nickel, carbon, copper, conductive glass and the like, and can be in the form of foil, holes, strips and nets, and the thickness of the positive current collector is 1-50 mu m.
The positive electrode active material layer further comprises a conductive agent, but not a binder, the conductive agent comprises one or more of acetylene black, carbon nanotubes, carbon fibers and carbon black, the proportion of the solid electrolyte is 0.01-10 wt.%, preferably 0.02-5 wt.%, and the proportion of the conductive agent is 0.1-20 wt.%, preferably 1-10 wt.%, based on the mass in the positive electrode active material layer. The thickness of the positive electrode layer is 10-300 μm.
According to the solid-state battery provided by the application, the negative electrode current collector is made of copper, stainless steel, nickel, carbon, conductive glass and the like, can exist in the form of foil, holes, strips and nets, and has the thickness of 1-50 μm.
A second object of the present application is to provide a method for manufacturing a solid-state battery, the method comprising:
s1, providing a positive electrode layer, wherein the positive electrode layer comprises a positive electrode current collector and a positive electrode active material layer located on the surface of the positive electrode current collector, and the positive electrode active material layer comprises positive electrode active particles and first solid electrolyte particles; heating the positive electrode layer to completely melt the first solid electrolyte particles in the positive electrode layer;
s2, providing a composite layer, wherein the composite layer comprises a negative electrode current collector and a solid electrolyte layer located on the surface of the negative electrode current collector, and the solid electrolyte layer comprises second solid electrolyte particles; heating the composite layer to completely melt the second solid electrolyte particles in the composite layer;
and S3, laminating the positive electrode layer melted in the step S1 and the composite layer melted in the step S2, controlling the laminating time of the positive electrode layer and the composite layer to be 1-300S, and then quenching to obtain the solid-state battery.
Step S1 and step S2 are not in sequence, and step S1 may be performed first, step S2 may be performed second, and step S3 may be performed last, or step S2 may be performed first, step S1 may be performed next, and step S3 may be performed last; or simultaneously performing the steps S1, S2, and S3.
Step S1 is to obtain a molten positive electrode layer, step S2 is to obtain a molten solid electrolyte layer, and step S3 is to laminate the molten positive electrode sheet and the molten solid electrolyte layer together to obtain a solid battery, the solid electrolyte layer and the positive electrode layer being separately molten and then laminated together. If the positive electrode layer and the composite layer are laminated together before heating, the assembled solid-state battery is heated to completely melt the first solid-state electrolyte particles and the second solid-state electrolyte particles, and in the process, the melting time needs to be accurately controlled, the melting time is too short, only local melting occurs, and the density of the solid-state battery is improved very limitedly; the melting time is too long, and the first solid electrolyte and the second solid electrolyte which are melted are easy to flow, so that the battery is easy to generate short circuit, and the preparation process of the battery is relatively uncontrollable. According to the preparation method, the solid electrolyte layer and the positive electrode layer need to be separately melted, so that the first solid electrolyte and the second solid electrolyte can be fully melted in a wide time period, and the problem of short circuit of the battery caused by diffusion between the solid electrolyte layer and the positive electrode layer is avoided. When the molten positive plate and the molten solid electrolyte layer are assembled, the combination time of the molten positive plate and the molten solid electrolyte layer is accurately controlled, the short circuit of the battery caused by overlong combination time is avoided, and although the control time is also needed in the process, the control time is easier than that of the melting process.
The preparation method of the positive electrode layer is not particularly limited, a slurry coating method can be used, and specifically, the slurry coating method is adopted, namely, the positive electrode active particles and the first solid electrolyte particles are dissolved in a solvent to prepare positive electrode slurry, and then the positive electrode slurry is coated on the surface of a positive electrode current collector and dried to obtain the positive electrode layer; the method of hot pressing can also be adopted, and specifically, the method of hot pressing is adopted, namely, after the positive active particles and the first solid electrolyte particles are uniformly mixed, the positive active particles and the first solid electrolyte particles are hot pressed with a positive current collector to form a positive plate; the hot pressing temperature is 150-300 ℃, the hot pressing time is 5min-2h, and the hot pressing pressure is 10-1000 MPa, so that the compactness of the positive plate is high, the internal gaps are few, the compactness of the positive plate can be further improved in the subsequent melting process, preferably, the positive plate layer is prepared in a hot pressing mode, slurry coating influences the compactness, in the melting and assembling process, the non-compact positive plate layer is easy to diffuse and generate short circuit, and compared with the slurry coating method, the hot pressing method is more compact in the prepared positive plate layer.
The preparation method of the composite layer is not particularly limited, and the preparation method can be the slurry coating method or the hot pressing method, preferably adopts the slurry coating method, because the negative active material layer does not exist in the composite layer, the second solid electrolyte particles can be completely melted during heating, so that the influence factor of compactness can not be influenced by the negative active material layer, and the slurry coating method is adopted at the moment, so that large-scale production is facilitated, and specifically, the second solid electrolyte slurry obtained by dissolving the second solid electrolyte particles in a solvent is coated on the surface of a negative current collector and dried to obtain the composite layer; the solvent is one or more of NMP, ethanol, acetone, benzene and toluene.
The heating temperature in step S1 of the preparation method provided herein should be not lower than the melting point of the first solid electrolyte and lower than the melting point of the positive electrode active particles, preferably 600 ℃ to 850 ℃, and the heating time is not particularly limited herein, as long as the first solid electrolyte can be completely melted, preferably 10min to 2h, during which the first solid electrolyte can be completely melted.
According to the preparation method provided by the present application, the heating temperature in step S2 should not be lower than the melting point of the second solid electrolyte, preferably the heating temperature is 600 ℃ to 850 ℃, the heating time is not particularly limited in the present application as long as the second solid electrolyte can be completely melted, and preferably the heating time is 20min to 12 h.
The heating mode is not particularly limited, and the heating mode can be heating by a conventional high-temperature furnace, or heating modes such as electric spark, high-energy microwave, plasma, laser and the like.
According to the preparation method provided by the application, the time for combining the melted positive electrode and the melted solid electrolyte layer in the step S3 is reduced as much as possible before the positive electrode and the melted solid electrolyte layer are cooled, but the melted positive electrode sheet and the melted solid electrolyte layer are ensured to be spread and contacted sufficiently, preferably, the time for laminating the melted positive electrode sheet and the melted composite layer is 1-300S, and the cooling rate is 5-100 ℃/S. The cooling rate is controlled so that the molten solid electrolyte layer can maintain a high-density melt-integrated state at a high temperature, and the melt-integrated solid electrolyte layer does not crack due to crystallization, so that the internal contact is poor.
Preferably, the quenching mode is air quenching, because the cooling rate requirement of quenching can be met, the generation of crystallization is inhibited, and the operation difficulty can be reduced.
A second object of the present application is to provide a solid-state battery produced by the above method.
A third object of the present application is to provide an electric vehicle including the solid-state battery provided above.
The invention is further described below using specific examples.
Example 1
(1) Manufacture of composite layer of negative electrode A and solid electrolyte E
The solid electrolyte described in this example has the following composition percentages: with 75Li2S-25P2S5For example.
The manufacturing process comprises the following steps: in a glove box under argon atmosphere, Li in a stoichiometric ratio2S（7.03g），P2S5(11.33 g) are mixed and then added into a 50ml sealed ball milling tank to be ball milled for 8h at 500rpm, then the mixture is taken out and ground into powder, the powder is placed into a 50g toluene solution, then the solid electrolyte slurry is heated and stirred, the solid electrolyte slurry is continuously coated on a negative current collector A, the coating thickness is 70 mu m, 333K is dried to obtain composite EA, the composite EA is cut into pieces with the size of 100 mm (length) × 100 mm (width), and the cut EA is placed on a hot plate to be heated to 700 ℃ to be melted and spread for 30min to be reserved for use.
(2) Production of Positive electrode sheet C
The positive active particles are LiCoO2The surface is coated with LiNbO3. 270mg of coated LiCoO2The positive electrode active particles were mixed with 15mg of a conductive agent (mass fraction: 5%) and 15mg of 75Li2S-25P2S5Uniformly mixing the solid electrolyte (5 wt%) in a grinding instrument, hot-pressing with the positive current collector at 200MPa and 250 deg.C for 30min to obtain positive plate C with a thickness of 150 μm, and preheating in a muffle furnace at 700 deg.C10min。
(3) Assembly of CEA
And (3) laminating the molten composite layer EA and the preheated positive plate C together, enabling the positive active material layer to be opposite to the solid electrolyte layer, and quenching in the air after 1min to obtain the solid battery CEA, wherein the cooling rate is about 30 ℃/S and is recorded as S1.
Example 2
A solid-state battery was produced in the same manner as in example 1, except that the heating time of EA in step (1) was 20min and the heating time in step (2) was 10min, and the resultant battery was denoted as S2.
Example 3
A solid-state battery was produced in the same manner as in example 1, except that the heating time of EA in step (1) was 12 hours and the heating time in step (2) was 2 hours, and the resultant battery was denoted as S3.
Example 4
A solid-state battery was produced in the same manner as in example 1, except that the heating temperature of EA in step (1) was 600 ℃, and the heating temperature in step (2) was 600 ℃, and the resultant battery was denoted as S4.
Example 5
A solid-state battery was produced in the same manner as in example 1, except that heating temperature of EA in step (1) was 850 ℃, and heating temperature in step (2) was 850 ℃, and the obtained battery was denoted as S5.
Example 6
A solid-state battery was produced in the same manner as in example 1, except that, in the step (3), the molten composite layer EA and the preheated positive electrode sheet C were laminated together for 1S, and the temperature was lowered to cool, and the battery obtained was denoted as S6.
Example 7
A solid-state battery was produced in the same manner as in example 1, except that, in the step (3), the molten composite layer EA and the preheated positive electrode sheet C were laminated together for 5 minutes, and the temperature was lowered to cool, and the battery obtained was denoted as S7.
Example 8
A solid-state battery was produced by the same procedure as in example 1, except that:
the solid electrolyte used in step (1) and step (2) was 30wt.% LiI, 70wt.% 0.75Li2S-0.25P2S5The obtained battery was designated as S8.
Example 9
A solid-state battery was produced by the same procedure as in example 1, except that:
the solid electrolyte used in step (1) and step (2) was 2wt.% Li3PO498 wt.% of 0.75Li2S-0.25P2S5The obtained battery was designated as S9.
Example 10
A solid-state battery was produced by the same procedure as in example 1, except that:
the solid electrolyte used in step (1) and step (2) is Li3OCl, cell obtained, S10.
Comparative example 1
(1) Manufacture of composite layer of negative electrode A and solid electrolyte E
The solid electrolyte described in this example has the following composition percentages: with 75Li2S-25P2S5For example.
The manufacturing process comprises the following steps: in a glove box under argon atmosphere, Li in a stoichiometric ratio2S（7.03g），P2S5(11.33 g) was mixed and ball milled at 500rpm for 8 hours in a 50ml sealed ball mill jar, then taken out and ground into a powder and placed in a 50g toluene solution, then heated and stirred to a stable, uniform solution which was continuously coated onto the negative current collector a at a coating thickness of 70 μm and dried at 333K to give EA cut to a size of 100 mm (length) × 100 mm (width).
(2) Production of Positive electrode sheet C
The positive active particles are LiCoO2The surface is coated with LiNbO3. 270mg of coated LiCoO2The positive electrode active particles were mixed with 15mg of a conductive agent (mass fraction: 5%) and 15mg of 75Li2S-25P2S5And (3) uniformly mixing the solid electrolyte (the mass fraction is 5%) in a grinding instrument, and hot-pressing the solid electrolyte and a positive nickel current collector together at the temperature of 250 ℃ under 200MPa for 30min to form a sheet to obtain a positive plate C, wherein the thickness of the positive active material layer is 150 mu m.
(3) Assembly of CEA
And laminating the composite layer EA and the positive plate C together to obtain a solid battery CEA, enabling the positive active material layer to be opposite to the solid electrolyte layer, heating the CEA for 30min, cooling, wherein the cooling rate is about 30 ℃/s, and finally obtaining the battery recorded asDS 1.
Comparative example 2
A solid-state battery was produced in the same manner as in example 1, except that the melt spreading time of EA in step (1) was 5min, the preheating time of the positive electrode sheet C was shortened to 1min in step (2), and the finally obtained battery was denoted as DS 2.
Comparative example 3
The positive active particles are LiCoO2The surface is coated with LiNbO3. 270mg of coated LiCoO2The positive electrode active particles were mixed with 15mg of a conductive agent (mass fraction: 5%) and 15mg of 75Li2S-25P2S5And uniformly mixing the solid electrolyte (the mass fraction is 5%) in a grinding instrument, cold-pressing the solid electrolyte and a positive nickel current collector for 30min at the temperature of 25 ℃ under 200MPa to obtain a positive plate C, wherein the thickness of a positive active material layer is 150 mu m, then adding 150mg of the solid electrolyte, continuously cold-pressing, pressing the positive plate C and the solid electrolyte E together, the thickness of a solid electrolyte layer is 100 mu m, placing a LiIn alloy plate on the other side of the solid electrolyte, pressurizing and assembling to obtain a solid battery, and finally obtaining the battery which is recorded asDS 3.
Comparative example 4
The positive active particles are LiCoO2The surface is coated with LiNbO3. 270mg of coated LiCoO2The positive electrode active particles were mixed with 15mg of a conductive agent (mass fraction: 5%) and 15mg of 75Li2S-25P2S5The solid electrolyte (5 percent by mass) is put into a grinding instrument to be uniformly mixed and is cold-pressed for 30min together with the positive nickel current collector under the pressure of 200MPa and the temperature of 25 DEG to obtain the electrolyteAnd (3) slicing to obtain a positive electrode sheet C, wherein the thickness of the positive electrode active material layer is 150 micrometers, then adding 150mg of solid electrolyte, continuously cold-pressing, pressing the positive electrode sheet C and the solid electrolyte E together, wherein the thickness of the solid electrolyte layer is 100 micrometers to obtain a composite layer CE of the positive electrode layer and the solid electrolyte layer, and heating the composite layer CE in a muffle furnace at 700 ℃ for 30 min. After cooling, lithium metal was attached to the solid electrolyte layer side as a negative electrode, and a solid battery was assembled, and the battery finally obtained was designated as DS 4.
Comparative example 5
A solid-state battery was manufactured in the same manner as in example 1, except that, in the step (1), a negative electrode active slurry layer was coated on the surface of the negative electrode current collector before the solid-state electrolyte slurry, which was prepared by mixing 9g of graphite as the negative electrode active particles and 1g of 75Li as the solid-state electrolyte particles, was coated on the negative electrode current collector a2S-25P2S5Dispersed in a solvent to prepare a negative electrode active paste, the coating thickness of the negative electrode active paste was 100 μm, and the obtained battery was recorded as DS 5.
Comparative example 6
A solid-state battery was produced in the same manner as in example 1, except that, in the step (3), the molten composite layer EA and the preheated positive electrode sheet C were laminated together for 20min, and the temperature was lowered to cool, whereby a battery was obtained, which was designated as DS 6.
Performance testing
The following tests were carried out for S1-S11 of the solid-state battery, and DS 1-DS 5 of the solid-state battery:
(1) electrochemical impedance testing
The test was carried out using an electrochemical workstation model zahnernim 6, germany, under the following test conditions: the room temperature was 25 ℃ and the scanning frequency ranged from 0.01Hz to 1 MHz, the amplitude was 12.5 mV, and the results are shown in Table 1.
(2) Measurement of Density
The calculation method is referred to the specification and is not described herein again.
(3) Measurement of Charge-discharge cycle Performance
The batteries prepared in each example and comparative example were 20 batteries, and the batteries were subjected to charge and discharge cycle tests at 0.1C, 1C, and 5C, respectively, on a LAND CT 2001C secondary battery performance testing apparatus at 298 ± 1K. The method comprises the following steps: standing for 10 min; charging at constant voltage to 4.2V/0.1C, and cutting off; standing for 10 min; constant current discharge is respectively carried out at 0.1C, 1C and 5C until the voltage reaches 1.5V, namely 1 cycle. The step is repeated, when the battery capacity is lower than 80% of the first discharge capacity in the circulation process, the circulation is terminated, the circulation times are the circulation life of the battery, each group is averaged, and the data of the parameters and the average first discharge capacity of the battery are shown in the following table 1.
(4) Observation by Scanning Electron Microscope (SEM)
The cross-sectional morphology of the all-solid batteries obtained in example 1 and comparative examples 2 and 3 was observed using a scanning electron microscope using a JEOL JSM-5610 LV.
(5) Volumetric energy density
Measurement of volume V of solid-state cell by Archimedes method0Volumetric energy density = C1/V0，C1The first discharge capacity.
Fig. 1 is an SEM image of the preparation of example 1, and it can be seen from the SEM image that the solid electrolyte in the positive electrode layer is coated on the surface of the positive electrode active particles and/or filled between the positive electrode active particles in a state of being completely melted and then quenched, and the positive electrode active particles are bonded by the solid electrolyte very tightly without any gap on the premise that the SEM magnification is 1000; the solid electrolyte layer has no obvious particles and is very smooth, and the amorphous state of the solid electrolyte which is connected together in a large area at high-temperature melting is completely reserved without gaps; the contact between the positive electrode layer and the solid electrolyte layer is very tight and seamless, the inside of the whole solid battery can hardly see a gap or a crack, and the solid battery is very compact; fig. 2 is an SEM image of comparative example 3, where only 158 times magnification still shows a distinct boundary between the positive electrode layer and the negative electrode layer, the solid electrolyte layer is rough and uneven, and solid electrolyte particles are clearly visible, as shown in fig. 3, where the SEM magnification is further increased to 500 times, there are distinct gaps between the positive electrode active particles and the positive electrode active particles, and there are distinct gaps between the solid electrolyte particles and the solid electrolyte; as shown in fig. 4, when the positive electrode layer is enlarged by 1000 times, the positive electrode active particles are arranged very sparsely, the gaps between the particles are more obvious, and even many cracks occur. Fig. 5 is an SEM image of comparative example 2, and in comparative example 2, the melting time is shortened based on example 1, and the positive electrode layer and the solid electrolyte layer are partially melted and partially bonded together, but it is clear that the solid electrolyte layer is not completely melted, particles are still clear, and the inside of the solid-state battery has large gaps and is not dense.
As can be seen from the test results of table 2, the improved overall performance of the solid-state battery of the present invention is significantly better than the comparative example. Comparative examples 1 and 4 were assembled and then heated, and the batteries were easily short-circuited. Comparative example 2 compared with example 1, the time for heating and melting was shortened, the solid electrolyte was partially melted, the compactness of the battery was significantly insufficient, and the battery was easily short-circuited since the negative electrode was directly used as the negative electrode current collector. The comparison results of comparative example 5 and example 1 show that even though the separate melting of the positive electrode layer and the negative electrode layer is achieved, a short circuit still occurs if the solid electrolyte and the negative electrode layer are melted, and thus the solid electrolyte and the positive electrode active material layer and the negative electrode active material must be separately melted and assembled in order for the battery not to be short-circuited. As is clear from comparison between comparative example 6 and example 1, when the molten positive electrode sheet and composite layer were assembled, short-circuiting was relatively likely to occur if the lamination time of the two was long, and therefore, it was necessary to precisely control the lamination time of the composite layer and the positive electrode sheet.
TABLE 1
Claims (13)
1. The solid-state battery is characterized by comprising a positive electrode layer, a solid-state electrolyte layer positioned on the surface of the positive electrode layer and a negative electrode current collector positioned on the surface of the solid-state electrolyte layer; the positive electrode layer comprises a positive electrode current collector and a positive electrode active material layer positioned on the surface of the positive electrode current collector, the positive electrode active material layer comprises positive electrode active particles and a first solid electrolyte, and the first solid electrolyte is coated on the surfaces of the positive electrode active particles and/or filled among the positive electrode active particles in a state of complete melting and then quenching; the solid electrolyte layer comprises a second solid electrolyte which is clamped between the positive electrode layer and the negative electrode current collector in a state of complete melting and then quenching; the density of the solid-state battery is 96-100%.
2. The solid-state battery according to claim 1, wherein the electrochemical impedance of the solid-state battery is 1 to 100 Ω.
3. The solid-state battery according to claim 1, wherein the solid-state battery has a volumetric energy density of 1000-1500 Wh/L.
4. The solid-state battery according to claim 1, wherein the first solid-state electrolyte and the second solid-state electrolyte are selected from one or more of a sulfur-based solid-state electrolyte, an anti-perovskite type solid-state electrolyte, an NASICON type solid-state electrolyte, and a perovskite type solid-state electrolyte.
5. The solid-state battery according to claim 1, further comprising a flux in the positive electrode layer and/or the solid electrolyte layer, wherein the flux is LiI, LiBr, LiF, Li2O，P2Se5，P2O5ZnO and Li3PO4One or more of (a).
6. A method for manufacturing a solid-state battery, characterized by comprising the steps of:
s1, providing a positive electrode layer, wherein the positive electrode layer comprises a positive electrode current collector and a positive electrode active material layer located on the surface of the positive electrode current collector, and the positive electrode active material layer comprises positive electrode active particles and first solid electrolyte particles; heating the positive electrode layer to completely melt the first solid electrolyte particles in the positive electrode layer;
s2, providing a composite layer, wherein the composite layer comprises a negative electrode current collector and a solid electrolyte layer located on the surface of the negative electrode current collector, and the solid electrolyte layer comprises second solid electrolyte particles; heating the composite layer to completely melt the second solid electrolyte particles in the composite layer;
and S3, laminating the positive electrode layer melted in the step S1 and the composite layer melted in the step S2, controlling the laminating time of the positive electrode layer and the composite layer to be 1-300S, and then quenching to obtain the solid-state battery.
7. The method for manufacturing a solid-state battery according to claim 6, wherein the method for manufacturing the positive electrode layer comprises the steps of uniformly mixing positive electrode active particles and first solid electrolyte particles, and then hot-pressing the mixture with a positive electrode current collector to form a positive electrode sheet; the hot pressing temperature is 150-300 ℃, the hot pressing time is 5min-2h, and the hot pressing pressure is 10-1000 MPa.
8. The method for manufacturing a solid-state cell according to claim 6, wherein the composite layer is manufactured by coating a second solid-state electrolyte slurry obtained by dissolving second solid-state electrolyte particles in a solvent on the surface of a negative current collector and drying the coating to obtain the composite layer; the solvent is one or more of NMP, ethanol, acetone, benzene and toluene.
9. The method for manufacturing a solid-state battery according to claim 6, wherein the heating temperature in step S1 is 600 ℃ to 850 ℃, and the heating time is 10min to 2 h; the heating temperature in the step S2 is 600-850 ℃, and the heating time is 20min-12 h.
10. The method for producing a solid-state battery according to claim 6, wherein the quenching rate is 5 ℃/s to 100 ℃/s.
11. The method for producing a solid-state battery according to claim 6, wherein the quenching is air quenching.
12. A solid-state battery, characterized in that it is produced by the method according to any one of claims 6 to 11.
13. An electric vehicle characterized by comprising the solid-state battery according to any one of claims 1 to 5 and 12.
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