CN112670483A - Positive plate, positive polar plate and solid-state battery - Google Patents
Positive plate, positive polar plate and solid-state battery Download PDFInfo
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Abstract
The invention provides a positive plate, a positive plate and a solid-state battery. The raw material components for preparing the positive plate comprise 60-98% of active electrode material, 1-15% of electronic conductive agent, 0.2-10% of auxiliary agent and 0.8-15% of ionic conductive agent. The positive plate is formed by compounding a positive plate and a current collector layer by hot rolling. The solid-state battery is assembled by a positive plate layer consisting of a positive plate, a solid-state electrolyte layer and a negative plate lamination sheet consisting of a lithium metal negative plate in sequence. The positive plate has low porosity; the active electrode material, the ionic conductive agent, the auxiliary agent and the like are adopted, so that the transference number and the diffusion rate of lithium ions can be improved, and the conductivity and the battery multiplying power are improved; the preparation process adopts a solvent-free dry process, effectively reduces interface contact impedance in the solid-state battery, constructs an integrated electrode with both electronic and ionic conduction networks, realizes electrode-solid electrolyte integrated molding, and promotes the early realization of industrialization of the solid-state battery.
Description
Technical Field
The invention belongs to the technical field of solid-state batteries, and relates to a positive plate, a positive plate and a solid-state battery.
Background
The solid-state battery has the excellent characteristics of ultrahigh safety, high energy density, high-integration manufacturing and grouping modes and the like, is a medium-long term technical route and even an ultimate technical scheme of a high-performance lithium battery, and has wide application prospects in the fields of high-end consumer electronics, new energy power batteries and the like.
In order to realize the scale application of the solid-state battery, breakthrough is urgently needed in part of key problems. Compared with a liquid battery, the solid battery has a core difference that the interface is a solid-solid interface, including interfaces between different components in the electrode and the interface between the electrode and an electrolyte, and has common problems of high interface impedance, interface separation caused by volume change in the charge and discharge process, interface degradation evolution in the cycle process and the like. For the interface between the electrode and the electrolyte, the interface impedance can be effectively reduced by sputtering, co-firing, spraying, wetting the interface with polymer or solvent in the literature and the patent, for example, the literature (j.power Sources 325,2016,584-590) proposes to calcine the anode and the solid electrolyte, and generate a new interface through chemical reaction to realize the connection between the electrode and the electrolyte, thereby reducing the interface impedance; the publication No. CN108336402A uses a high molecular polymer as an interface buffer layer, and improves the interface contact of the ceramic-based solid electrolyte and reduces the interface impedance on the premise of ensuring a certain mechanical strength.
However, for the problem of the contact between the inside of the electrode, i.e. the bulk phase interface, at present, the positive electrode, the conductive agent, the solid electrolyte, the binder, etc. are generally physically mixed, and then if the solid electrolyte is an oxide or polymer type, the electrode sheet for the solid battery is obtained by coating, while for the sulfide type solid electrolyte, the electrode sheet is difficult to obtain by wet coating due to the problems of harsh environmental requirements, difficult solvent selection, etc., and generally the electrode sheet with a small area is obtained by compacting the electrode sheet under a great pressure in a laboratory. The method still uses the existing main wet film-forming method, namely, all powder materials are made into slurry by adopting a binder solution or emulsion, then film-forming treatment is carried out, a solvent in the binder solution or emulsion needs to be dried in the film-forming treatment process, the solvent volatilization process is a necessary step for pore-forming required by the porous electrode, but for the solid battery, an active material is required to be in close contact with components such as an ion-conducting solid electrolyte and a conductive agent playing an electron-conducting role, so that a sufficient and unblocked electron and ion path is constructed, in other words, the electrode required by the solid battery is an integrated electrode with both electron conduction and ion conduction and low porosity.
Meanwhile, the solid-state battery uses ceramic-based solid electrolyte with higher density (more than or equal to 3 g/cm)3) Replacing electrolyte with lower density (approximately equal to 1.3 g/cm)3) However, in the case of a solid-state battery using the same positive and negative electrode systems, the energy density is rather decreased, and therefore, in order to improve the solid-state battery using the same electrode system, it is effective to prepare a highly compacted thick electrode. Since conventional wet coating processes involve solvent drying processes, it is highly desirable to coat coatings with thicknesses in excess of a certain thickness (e.g., 150 microns and above)The formed electrode is cracked, so the current wet coating process has great limitation on the preparation of the thick electrode. At the same time, some battery manufacturers have attempted to increase the electrode thickness to increase the energy density of the liquid cell. Although the thicker the thickness and the higher the compaction, the higher the energy density of the battery theoretically can be improved, the liquid battery has a subsequent electrolyte injection link, which brings a series of problems to the infiltration and formation of electrolyte in the later period, such as multiple times of electrolyte injection, prolonged standing time, poor battery production efficiency, and the performance problems of poor battery infiltration, increased internal resistance, lithium precipitation and the like. Therefore, liquid state batteries with increased electrode thickness and compaction to increase energy density still require overall and system considerations in terms of efficiency, manufacturing feasibility, cost, and the like.
In addition, the current coating process not only causes environmental pollution due to the use of a large amount of solvent (nitrogen methyl pyrrolidone or water), but also needs a drying link with high energy consumption, increases the investment of drying and solvent recovery equipment, and inevitably introduces impurities to bring negative effects on the performance of the battery. To address the above drawbacks, some capacitor and battery manufacturers have attempted to introduce the development of solvent-free processes. Publication No. CN102629681A proposes a process method based on mixing-jet milling-extrusion, which is used for preparing an activated carbon electrode for a capacitor, thereby avoiding the influence of impurity introduction on the performance of the capacitor and simultaneously reducing the energy consumption; publication No. CN107732137A proposes a process based on air flow mixing-vertical rolling-horizontal rolling, which is used for preparing a lithium titanate cathode.
However, the related patents at present mainly solve the problems of uniform mixing of powder, continuous film formation, consistency control and the like faced by the solvent-free process, and the purpose of the solvent-free process is still to prepare a porous electrode for a liquid battery and make a polar plate thinner, so as to promote the sufficient infiltration of electrolyte and further ensure the cycle performance and rate capability of the battery; the porous electrode and the solid-liquid interface of the liquid battery obviously cannot exert the maximum benefit of the solid battery. For the low-porosity and ultra-thick integrated electrode (having both electron and ion conductive networks) used in the solid-state battery, there is still no relevant research, and the enlargeable process or method is less involved, so there is a need for a new design of electrode structure and preparation process of the solid-state battery, which can realize the maximum performance of the solid-state battery and realize the industrial application of the solid-state battery as soon as possible.
Disclosure of Invention
Based on the defects of the conventional liquid phase coating process and the problems that the porous electrode and the solid-liquid interface of the liquid battery block the performance of the solid battery, the first purpose of the invention is to provide a positive plate which has the integrated design of electronic conduction and ionic conduction and has the thickness of 200-500 mu m; the porosity is 1% -37%; the second purpose of the invention is to provide a preparation method of the positive plate; a third object of the present invention is to provide a positive electrode plate; a fourth object of the present invention is to provide a solid-state battery.
The purpose of the invention is realized by the following technical means:
in one aspect, the present invention provides a positive electrode sheet for a solid-state battery, wherein the positive electrode sheet is prepared from the following raw material components, by mass:
60 to 98 percent of active electrode material, 1 to 15 percent of electronic conductive agent, 0.2 to 10 percent of auxiliary agent and
0.8 to 15 percent of ion conductive agent.
In the positive electrode sheet, the thickness of the positive electrode sheet is preferably 200 to 500 μm; the porosity is 1-37%.
The positive plate has low porosity of 1-37%, preferably 1-20%, and can reduce the contact resistance between particles to the maximum extent.
In the above positive electrode sheet, preferably, the active electrode material is prepared by coating the surface of the active material with a ceramic-based ion conductor; the active electrode material accounts for 95-99.8% of the mass fraction of the active electrode material, and the ceramic-based ion conductor accounts for 0.2-5%.
In the positive electrode sheet, the coating thickness is preferably 3 to 300 nm; further preferably, the coating has a thickness of 3 to 50 nm.
In the above positive electrode sheet, preferably, the coating method includes, but is not limited to, a sol-gel method, a mechanical mixing method, a fluidized bed in-situ coating method, a spray drying method, or an ultrasonic atomization method; the coating method is a conventional coating method in the field.
In the positive electrode sheet described above, preferably, the ceramic-based ion conductor includes Li7La3Zr2O12(LLZO)、LixLa2/3- xTiO3(LLTO)(0<x<0.16)、Li1+xAlxTi2-x(PO4)3(LATP)(0.1＜x＜0.5)、LiAlO2(LAO) and Li7- xLa3Zr2-xMx012(M is Ta or Nb, 0.25 < x < 2) (LLZMO), but is not limited thereto.
In the above positive electrode sheet, preferably, the active material includes lithium nickel cobalt manganese oxide, lithium iron phosphate, lithium manganese oxide, lithium cobalt oxide, lithium manganese nickel oxide, lithium cobalt oxide, and LiNiO2But is not limited thereto.
The surface of the positive active material is coated with the ceramic-based ionic conductor to realize island-shaped coating on the surface of the positive material, and the particle size of the ceramic-based ionic conductor is preferably 100-200 nm.
The surface of the positive electrode active material is coated by the ceramic-based ion conductor, so that the transference number and the diffusion rate of lithium ions are improved, and the dissolution of some high-voltage positive electrode materials (such as lithium nickel cobalt manganese oxide transition metal) can be prevented.
In the positive electrode sheet, preferably, the auxiliary agent includes one or more of polypropylene alcohol, polyacrylic acid, polypropylene, polyethylene, polyacrylonitrile, polymethyl methacrylate, nitrile rubber, polyethylene carbonate, polypropylene carbonate, and polybutylene carbonate, but is not limited thereto.
In the positive plate, the use of a binder is cancelled, and the positive plate is replaced by an auxiliary agent with ionic conductivity and cohesiveness, so that the processability of the plate based on a dry process technology can be improved, the close contact of an active electrode material, the auxiliary agent, an ionic conductive agent and an electronic conductive agent is increased, the interface ionic conductivity of ceramic and polymer electrolyte is enhanced by virtue of the high ionic conductivity and/or bridging action of the positive plate, and the rate characteristic of a battery is improved.
In the above positive electrode sheet, preferably, the ionic conductive agent includes, by mass, 50% to 90% of a polymer matrix, 2% to 20% of a dopant, 3% to 15% of a small molecule ion conductor, and 5% to 15% of a lithium salt, based on 100% of the ionic conductive agent.
In the positive electrode sheet described above, preferably, the polymer matrix includes one or more of poly (m-phenylene sulfide) (PMPS), poly (p-phenylene sulfide) (PPS), and poly (dibenzothiophene sulfide) (PDTS), but is not limited thereto.
In the positive electrode sheet described above, preferably, the dopant includes one or more of tetraphenylporphyrin tetrasulfonic acid, 1,3,6, 8-pyrenetetrasulfonic acid tetrasodium salt, 1,4,5, 8-naphthaloyldiimide, benzenesulfonic acid, terephthalulfonic acid, and 4, 4' -biphenyldisulfonic acid, but is not limited thereto.
In the positive electrode sheet described above, preferably, the small molecule ion conductor includes one or more of Ethylene Carbonate (EC), diethyl carbonate (DEC), dimethyl carbonate (DMC), and succinonitrile, but is not limited thereto.
In the above positive electrode sheet, preferably, the lithium salt includes LiFP6、LiBF4、LiBOB、LiTFSI、LiFSI、LiDFOB、LiClO4And LiAsO4But are not limited thereto.
In the positive electrode sheet described above, preferably, the electron conductive agent includes one or more of Acetylene Black (AB), conductive carbon black (Super P), Carbon Nanotube (CNT), vapor deposition carbon fiber (VGCF), and Graphene (Graphene), but is not limited thereto.
In the positive plate, the ionic conductive agent is obtained by mixing a polymer matrix, a doping agent, a small molecular ion conductor and lithium salt. The inventors have found that the glass transition temperatures of the polymer matrices according to the invention are all high, and a comparison of the glass transition temperatures of the three polymer matrices according to the invention with that of PEO groups is given in Table 1.
Table 1:
as can be seen from table 1: compared with a PEO-based polymer fast ion conductor, the PEO-based polymer fast ion conductor has stronger polarity, the dielectric constant of the PEO-based polymer fast ion conductor is lower than that of the polymer ion conductor of the invention, indirectly, the polymer ion conductor of the invention is different from PEO and other segment lithium conducting, but similar to crystal lithium conducting, the carrier decoupling motion released from a polymer monomer greatly improves the dissociation degree of salt, and the structure and the properties result in that the polymer ion conductor (polymer matrix + doping agent) of the invention has higher ionic conductivity at room temperature.
The ionic conductive agent is also added with a micromolecule ionic conductor, which can realize effective infiltration among different components in the electrode and reduce the interface stress.
The lithium salt in the ionic conductive agent can further improve the transference number of lithium ions and is beneficial to improving the electrical conductivity, and the research of the inventor finds that the ionic conductive agent adopting multi-component lithium salt has a better promotion range than the lithium salt with single component, and the lithium salt in a combination form is preferably selected, for example, LiBF with the mass ratio of 1:14And lithium salts in a mixed form of LiDFOB.
On the other hand, the invention also provides a preparation method of the positive plate, which comprises the following steps:
mixing the active electrode material, the electronic conductive agent, the auxiliary agent and the ionic conductive agent according to the proportion by a dispersion machine, then shearing, extruding the materials, heating and rolling by a multi-stage roller to obtain the positive plate.
In the preparation method of the positive plate, a solvent-free method is adopted for powder mixing, namely a dry process. The preparation of the slurry for coating is carried out without using a solvent for dissolving the powder. Because no solvent is used, the method has no porosity and/or high porosity caused by solvent volatilization, eliminates the difficulty in selecting an ionic conductor by the solvent, effectively reduces the interface contact resistance in the solid-state battery, and simultaneously constructs the positive plate with integration of electronic conductivity and ionic conductivity, uniform bulk compaction density and controllable thickness and porosity.
In the preparation method, the mixing speed of the disperser is 1000-2200 rpm, and the dispersing time is 10 min-4 h.
In the preparation method, preferably, high-shear equipment is adopted for shearing, the shearing rotating speed is 10-40 rpm, and the shearing time is 20 min-2 h; preferably, the high shear device is an internal mixing device.
In still another aspect, the present invention further provides a positive electrode plate for a solid-state battery, wherein the positive electrode plate comprises the above positive electrode sheet and current collector layer;
the thickness of the positive plate is 200-500 mu m; the thickness of the current collector layer is 5-20 mu m;
the positive plate is formed by compounding a positive plate and a current collector layer by hot rolling.
In the above positive electrode plate, preferably, the current collector layer includes an aluminum foil and an aluminum plated product; and the surface of the current collector layer is provided with a glue coating layer, and the thickness of the glue coating layer is 1-3 mu m.
In the positive electrode plate, the rolling temperature of hot rolling is preferably 80-160 ℃, and the rolling speed is preferably 5-20 m/min.
The positive pole plate can be made to be very thick under the condition of not changing the multiplying power performance of the battery. However, for cylindrical or wound cells, the thickness of the positive electrode plate is generally not more than 1mm in this type of cell, considering the bending of the plate in the cell and the mechanical properties of the thick electrode and the load-bearing capacity of the current collector.
In yet another aspect, the present invention further provides a solid-state battery, wherein the solid-state battery is assembled by stacking 3 layers;
the lithium ion battery sequentially comprises an anode plate layer consisting of the anode plate, a solid electrolyte layer and a cathode plate layer consisting of a lithium metal cathode;
the thickness of the positive electrode plate layer is 206-520 μm;
the thickness of the solid electrolyte layer is 10-40 mu m;
the thickness of the negative electrode plate layer is 20-50 mu m.
In the solid-state battery, the negative pole plate layer is made of metal lithium, and compared with a negative pole material with higher specific capacity such as a silicon negative pole, the metal lithium has more advantages in energy density. In a liquid battery, when metal lithium is selected as a negative electrode, lithium dendrite is generated due to non-uniform current density, and the cycle and safety performance of the battery are affected. In the solid-state battery, the mechanical strength of the solid-state electrolyte can inhibit the generation of lithium dendrite, so that the metal lithium negative electrode plate has better matching property with the solid-state electrolyte.
In the solid-state battery, preferably, the solid-state electrolyte layer is obtained by uniformly mixing the polymer matrix, the dopant and the lithium salt, and extruding the mixture into a film through a melt extruder; the mass fraction of the solid electrolyte layer is 100%, the polymer matrix accounts for 65% -90%, the dopant accounts for 5% -20%, and the lithium salt accounts for 5% -15%.
The optional components of the polymer matrix, the dopant and the lithium salt in the solid electrolyte layer of the present invention are the same as those of the polymer matrix, the dopant and the lithium salt in the ionic conductive agent of the present invention. The polymer matrix and dopant are mixed and reacted by heating to create sites for transporting and migrating lithium ions, forming a polymer ion conductor.
In the solid-state battery, the melt extrusion temperature is preferably 80 to 160 ℃.
The invention has the beneficial effects that:
1. the positive plate and the positive plate of the invention are as follows:
(1) the active electrode material is prepared by coating the surface of the active material by adopting a ceramic-based ion conductor, so that the improvement of the transference number and the diffusion rate of lithium ions are realized, and the dissolution of some high-voltage positive electrode materials (such as lithium nickel cobalt manganese oxide transition metal) can be prevented;
(2) the use of a binder is cancelled, and the electrode plate is replaced by an auxiliary agent with ionic conductivity and cohesiveness, so that the processability of the electrode plate based on a dry process is improved, the close contact between the active main material and the ionic conductive agent and the electronic conductive agent is increased, the interface ionic conductivity of the ceramic and the polymer electrolyte is enhanced by virtue of the high ionic conductivity and/or the bridging action of the electrode plate, and the rate characteristic of the battery is improved;
(3) the ionic conductive agent is composed of a polymer matrix, a doping agent, a small molecular ionic conductor and lithium salt. The mixture of the polymer matrix and the dopant of the invention has higher glass transition temperature; the micromolecular ionic conductor can realize effective infiltration among different components in the electrode, and reduce the interface stress; the lithium salt can further improve the transference number of lithium ions, and is beneficial to improving the electrical conductivity.
2. The invention discloses a preparation process of a positive plate and a positive polar plate, which comprises the following steps:
(1) the invention introduces the solvent-free continuous pole piece processing technology into the solid-state battery for the first time, and adopts the solvent-free technology (dry technology) to mix the powder, thereby eliminating the difficulty of selecting the solvent for the ionic conductor; because no solvent is used, the porosity and/or high porosity caused by solvent volatilization do not exist, and the prepared positive plate has low porosity and can reduce the contact resistance between material particles to the greatest extent; and performing multi-stage hot rolling on the powder obtained by dry mixing, wherein the obtained pole piece has a self-supporting characteristic, and the uniformity of the compacted density of the pole piece is greatly improved compared with that of the pole piece coated by a wet method. Therefore, the process can simultaneously construct the integrated electrode with the electronic and ionic conductive networks and the ultra-thick electrode plate with adjustable thickness.
(2) The method of the invention omits the links of electrode drying and later-stage liquid injection, is directly used for assembling to form a solid-state battery, has a wide potential window and low interface impedance, realizes double significant improvement of safety and energy density, shortens standing and formation time, simplifies the process, reduces equipment investment and energy consumption, and improves production efficiency.
3. The solid-state battery of the present invention:
the solid-state battery realizes the structural design of the composite electrode formed by integrally forming the electrode and the solid-state electrolyte, adapts to the positive electrode and the negative electrode with high specific energy, avoids the influence of external solvents/impurities, improves the safety, the electrical property and other comprehensive properties of the solid-state battery, and promotes the early realization of industrialization of the solid-state battery.
Drawings
Fig. 1 is a schematic view of a microscopic partial view of a positive electrode sheet according to the present invention (1 represents a positive electrode material, 2 represents a ceramic-based ion conductor, 3 represents an electron conductive agent, 4 represents an ion conductive agent, and 5 represents an auxiliary agent).
Fig. 2 is an SEM image of the positive electrode sheet in example 1 of the present invention.
Fig. 3 is a schematic structural view of a solid-state battery in example 1 of the present invention (1 denotes a positive electrode sheet layer, 2 denotes a solid electrolyte layer, and 3 denotes a negative electrode sheet layer).
Fig. 4 is a comparison graph of first charge and discharge curves of example 1, comparative example 1 and comparative example 6 of the present invention.
FIG. 5 is a graph comparing the number of cycles and capacity retention rate of example 1, comparative example 2, comparative example 3 and comparative example 5 of the present invention.
Fig. 6 is an SEM image of the positive electrode sheet after the solid-state battery of example 1 of the present invention has been cycled for 200 cycles.
Detailed Description
The technical solutions of the present invention will be described in detail below in order to clearly understand the technical features, objects, and advantages of the present invention, but the present invention is not limited to the practical scope of the present invention.
Example (b):
the following embodiment provides a preparation process of a solid-state battery, and the specific preparation method is as follows:
1. preparing a positive plate and a positive polar plate:
(1) preparing raw materials:
active electrode material: by using ceramic-based ionic conductors Li1.3Al0.3Ti1.7(PO4)3(LATP) coating the surface of the single crystal nickel-cobalt-manganese oxide positive electrode material NCM811 by a spray drying method, wherein the coating thickness is 50nm, and obtaining the active electrode material.
The single crystal nickel cobalt manganese oxide positive electrode material NCM811 was directly used as the comparative active electrode material.
Electron conductive agent: single-walled carbon nanotubes.
Auxiliary agent: polypropylene carbonate.
Ion conductive agent: mixing poly-p-phenylene sulfide (PPS), tetraphenyl porphine tetrasulfonic acid, Succinonitrile (SN) and lithium salt according to a mass ratio of 80:10:5: 5. The lithium salt was prepared by mixing LiTFSI and LiDFOB (70: 30 wt%).
(2) The preparation process of the positive plate and the positive polar plate comprises the following steps:
mixing 94% of the active electrode material, 1% of the single-walled carbon nanotube as an electronic conductive agent, 2% of polypropylene carbonate as an auxiliary agent and 3% of the ionic conductive agent according to the mass percentage to obtain mixed powder;
uniformly mixing the mixed powder in advance by adopting a gravity-free mixing disperser, wherein the rotating speed is 2200rpm, the loading capacity is 65 percent, and the dispersing time is 2 hours; then shearing the mixture by an internal mixer to form a pulp mass, wherein the rotating speed is 40rpm, and a quadrangular spiral rotor is selected; the shearing time is 30 min; then, carrying out pulp cluster extrusion through a composite screw extruder to obtain a sheet with the thickness of 1 mm; and (4) obtaining the positive plates with different thicknesses and porosities by the hot rolling equipment and adjusting the gap between the rollers. Hot rolling is carried out on different positive plates obtained by the preparation method so as to realize the compounding with a current collector layer aluminum foil (the surface of which contains a glue coating layer with the thickness of 1-3 mu m), the rolling temperature is 80 ℃, the rolling speed is 12m/min, and a compounded positive plate 1# to 2# and a comparative positive plate 1# to 4# are obtained, the width is 310mm, and the thickness and the porosity are shown in table 2:
table 2: different positive pole plate information tables:
| positive electrode active material | Porosity of the material | Thickness of | |
| |
LATP-cladded NCM811 | 14％ | 280μm |
| |
LATP-cladded NCM811 | 15％ | 300μm |
| Comparison of |
NCM811 | 22％ | 300μm |
| Comparison of |
LATP-cladded NCM811 | 30％ | 450μm |
| Comparison of |
LATP-cladded NCM811 | 30％ | 480μm |
| Comparison of positive plate 4# | LATP-cladded NCM811 | 30％ | 500μm |
2. Preparation of solid electrolyte layer:
mixing a polymer matrix and a doping agent according to a certain proportion, adding lithium salt, uniformly mixing according to a specific proportion, and extruding by an extruder to form a film, wherein the extrusion temperature is 110 ℃, so as to obtain a solid electrolyte layer with the thickness of 35 mu m and the width of 315 mm.
According to different polymer matrixes, dopants and lithium salt combinations and different mixing ratios, samples of the solid electrolyte 1# to 5# are respectively obtained, as shown in Table 3:
table 3: table of different solid electrolyte layer information:
3. preparation of solid-state batteries:
and (3) stacking and assembling the prepared positive electrode plate, the solid electrolyte layer and the metal lithium negative electrode (the thickness is 50 mu m), and assisting a plurality of commonly used tabs for leading external current and an outer packaging sealing material to prepare the solid battery. Fig. 3 is a schematic structural view of the solid-state battery (1 denotes a positive electrode plate layer, 2 denotes a solid electrolyte layer, and 3 denotes a negative electrode plate layer).
The specific compositions and main results of examples 1 to 2 and comparative examples 1 to 6 are shown in Table 4:
table 4: different solid state battery information tables:
the related test method comprises the following steps:
(1) testing of ion conductivity of solid electrolyte:
the solid electrolyte is cut into 2cm multiplied by 2cm, and is placed between 2 steel sheets with the thickness of 1mm and the diameter of 1cm of SUS304, and the upper steel sheet and the lower steel sheet are respectively connected with a working electrode and a counter electrode of an electrochemical workstation. And selecting electrochemical alternating current impedance spectrum for testing, wherein the frequency range is 10 mHz-100 kHz. After reading the resistance value R, the ionic conductivity (delta: ionic conductivity; A cross-sectional area: d thickness of solid electrolyte) was determined from the value of delta d/AR
(2) Testing of porosity:
calculating the volume V1 of the positive plate with porosity of 0 under a certain surface density from the true density of each material, and the actual measured volume of the positive plate under a certain surface density is V2。V2-V1/V2X 100% is the porosity.
(3) Energy density and discharge gram capacity calibration:
the solid-state battery is charged and discharged for the first time at 0.1C in a range of 3.0-4.2V. And the second time of charging and discharging at 0.1C, and the energy of discharging divided by the weight of the battery is the energy density of the battery. The discharged capacity of the battery is the gram-discharge capacity of the battery when the weight of the positive electrode active material (NCM811) is the weight of the positive electrode active material. Similarly, the gram discharge capacity of 1C was also measured.
(4) Testing the cycle performance of the solid-state battery:
and (3) placing the solid-state battery in an environment at 25 ℃, and performing charge-discharge circulation at 0.5C/1C and between 3.0 and 4.3V. The decay of the discharge capacity was recorded.
Fig. 1 is a schematic view of a microscopic partial view of a positive electrode sheet (1 represents a positive electrode material, 2 represents a ceramic-based ion conductor, 3 represents an electron conductive agent, 4 represents an ion conductive agent, and 5 represents an auxiliary agent). As can be seen from fig. 1: the invention provides an integrated electrode structure design for a solid-state battery, wherein ceramic-based ion conductors are discretely distributed on the surface of a positive electrode material in an island-shaped coating mode, the rest part of the surface of the positive electrode material is filled and wrapped by an electronic conductive agent, the ionic conductive agent serves as a connecting bridge between the ceramic-based ion conductors, so that a three-dimensional ion conductive network is constructed, an auxiliary agent is filled in the electrode, on one hand, different component particles are bonded, and due to the ionic conductivity of the auxiliary agent and/or the bridging effect of the ceramic-based ion conductors and a polymer-based ion conductor is exerted, so that the interface ion conduction of an electrode body phase is enhanced.
Fig. 2 is an SEM image of the positive electrode sheet of example 1. As can be seen from fig. 2: the internal structure of the electrode with low porosity and uniformly distributed components can be obtained by using the process disclosed by the invention, and the expectation of the structural design shown in figure 1 is achieved.
As can be seen from table 3, a significant increase in ionic conductivity was achieved after the lithium salt was changed from a single component to a multi-component. The proportion of the polymer ion conductor is increased in the solid electrolyte, so that the ionic conductivity of the polymer ion conductor is further improved; but the mechanical properties of the solid electrolyte are affected because the ratio of the polymer ion conductor is too low. The combination of PMPS polymer monomer and chloro jade can improve the ionic conductivity of the solid electrolyte to 10-3And S/cm grade.
Table 4 shows that after increasing the discharge current, the capacity exertion of the solid-state batteries of examples 1 and 2 containing the solid-state electrolyte of the present invention is significantly higher than that of comparative examples 1 and 2 containing other solid-state electrolytes of comparative examples 1 and 2, the solid-state electrolyte of PEO is unstable at high voltage, consuming more active Li at the positive electrode, and the LLZTO/polyvinylidene fluoride interfacial resistance is large, affecting the discharge capacity at large current.
Fig. 4 is the first charge-discharge curves of example 1, comparative example 1 and comparative example 6, and it can be seen that the first gram discharge capacity of the PEO solid electrolyte is only 178mAh/g, and the first coulombic efficiency is about 78%, which indicates that the PEO solid electrolyte is unstable under high voltage, and part of lithium extracted from the positive electrode participates in the side reaction, thereby affecting the discharge capacity. From the charge and discharge curves of example 1 and comparative example 6, the prepared high compacted, low porosity positive electrode plate (example 1) and low compacted, high porosity (comparative example 6) were consistent in capacity exertion.
Fig. 5 is a comparison of cycle performance of example 1, comparative example 2, comparative example 3, and comparative example 5, and it can be seen that the charge and discharge cycles of example 1 can achieve the least attenuation within 200 cycles, indicating that the high compacted thick electrode can achieve long-term cycle stability due to the close contact between the electrode material and the electron conductive agent, the ion conductive agent. While comparative example 2 shows a normal cycle decay at the beginning, but a sudden capacity jump occurs, mainly due to the dominance of the ceramic-based solid electrolyte in LLZTO/PVDF and the continuous increase of the interface impedance. Comparative example 3 decay was faster although no diving occurred, since the lithium ion transport and transport ability of the NCM881 positive electrode material without LATP coating was significantly weaker than that of the NCM881 positive electrode active material with LATP coating of example 1. In contrast, in comparative example 5, since the porosity of the positive electrode plate is high, the electrode material is not in close contact with the electron conductive agent and the ion conductive agent, and further interfacial separation occurs during the cycle, resulting in a rapid increase in interfacial resistance, and thus rapid cycle decay occurs.
Fig. 6 is the surface of the lithium metal after 200 cycles of the solid-state battery of example 1, and it can be seen that no lithium dendrites are generated on the surface of the lithium metal.
Claims (10)
1. A positive plate for a solid-state battery is disclosed, wherein the positive plate is prepared from the following raw materials in percentage by mass of 100%:
60 to 98 percent of active electrode material, 1 to 15 percent of electronic conductive agent, 0.2 to 10 percent of auxiliary agent and 0.8 to 15 percent of ionic conductive agent.
2. The positive electrode sheet according to claim 1, wherein the thickness of the positive electrode sheet is 200 to 500 μm; the porosity is 1-37%.
3. The positive electrode sheet according to claim 1, wherein the active electrode material is prepared by surface coating the active material with a ceramic-based ionic conductor; by taking the mass fraction of the active electrode material as 100%, the active material accounts for 95% -99.8%, and the ceramic-based ion conductor accounts for 0.2% -5%;
preferably, the thickness of the coating is 3-300 nm; further preferably, the thickness of the coating is 3-50 nm;
preferably, the coating method comprises a sol-gel method, a mechanical mixing method, a fluidized bed in-situ coating method, a spray drying method or an ultrasonic atomization method;
preferably, the ceramic-based ion conductor comprises Li7La3Zr2O12、LixLa2/3-xTiO3(0<x<0.16)、Li1+xAlxTi2-x(PO4)3(0.1＜x＜0.5)、LiAlO2And Li7-xLa3Zr2-xMx012(M is Ta or Nb, 0.25 < x < 2);
preferably, the active material includes lithium nickel cobalt manganese oxide, lithium iron phosphate, lithium manganese oxide, lithium cobalt phosphate, lithium manganese nickel phosphate, lithium cobalt oxide, and LiNiO2One or more of (a).
4. The positive electrode sheet according to claim 1, wherein the auxiliary agent includes one or more of polypropylene alcohol, polyacrylic acid, polypropylene, polyethylene, polyacrylonitrile, polymethyl methacrylate, nitrile rubber, polyethylene carbonate, polypropylene carbonate, and polybutylene carbonate.
5. The positive electrode sheet according to claim 1, wherein the ionic conduction agent comprises 50-90% of a polymer matrix, 2-20% of a dopant, 3-15% of a small molecule ion conductor, and 5-15% of a lithium salt, based on 100% of the ionic conduction agent by mass;
preferably, the polymer matrix comprises one or more of poly (m-phenylene sulfide), poly (p-phenylene sulfide), and poly (dibenzothiophene sulfide);
preferably, the dopant comprises one or more of tetraphenyl porphine tetrasulfonic acid, 1,3,6, 8-pyrenetetrasulfonic acid tetrasodium salt, 1,4,5, 8-naphthaloyldiimide, benzenesulfonic acid, terephthalulfonic acid, and 4, 4' -biphenyldisulfonic acid;
preferably, the small molecule ion conductor comprises one or more of ethylene carbonate, diethyl carbonate, dimethyl carbonate and succinonitrile;
preferably, the lithium salt comprises LiFP6、LiBF4、LiBOB、LiTFSI、LiFSI、LiDFOB、LiClO4And LiAsO4One or more of them.
6. The positive electrode sheet according to claim 1, wherein the electron conductive agent includes one or more of acetylene black, conductive carbon black, carbon nanotubes, vapor deposited carbon fibers, and graphene.
7. The method for producing a positive electrode sheet according to any one of claims 1 to 6, comprising the steps of:
mixing the active electrode material, the electronic conductive agent, the auxiliary agent and the ionic conductive agent according to the proportion by a dispersion machine, then shearing, extruding the materials, heating and rolling by a multi-stage roller to obtain the positive plate.
8. The preparation method according to claim 7, wherein the mixing speed by a disperser is 1000-2200 rpm, and the dispersing time is 10 min-4 h;
preferably, high-shear equipment is adopted for shearing, the shearing rotating speed is 10-40 rpm, and the shearing time is 20 min-2 h; preferably, the high shear device is an internal mixing device.
9. A positive electrode plate for a solid-state battery, wherein the positive electrode plate comprises the positive electrode sheet according to any one of claims 1 to 6 and a current collector layer;
the thickness of the positive plate is 200-500 mu m; the thickness of the current collector layer is 5-20 mu m;
the positive plate is formed by compounding a positive plate and a current collector layer by hot rolling;
preferably, the current collector layer comprises an aluminum foil and an aluminum-plated product; the surface of the current collector layer is provided with a glue coating layer, and the thickness of the glue coating layer is 1-3 mu m;
preferably, the rolling temperature of hot rolling is 80-160 ℃, and the rolling speed is 5-20 m/min.
10. A solid-state battery, wherein the solid-state battery is assembled by 3-layer lamination;
a positive electrode plate layer comprising the positive electrode plate according to claim 9, a solid electrolyte layer, and a negative electrode plate layer comprising a lithium metal negative electrode in this order;
the thickness of the positive electrode plate layer is 206-520 μm;
the thickness of the solid electrolyte layer is 10-40 mu m;
the thickness of the negative electrode plate layer is 20-50 microns;
preferably, the solid electrolyte layer is obtained by uniformly mixing a polymer matrix, a doping agent and a lithium salt, and extruding the mixture into a film through a melt extruder; the mass fraction of the solid electrolyte layer is 100%, the polymer matrix accounts for 65% -90%, the dopant accounts for 5% -20%, and the lithium salt accounts for 5% -15%;
preferably, the temperature of the melt extrusion is 80-160 ℃.
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