CN112713266B - Negative electrode slurry and application thereof - Google Patents

Negative electrode slurry and application thereof Download PDF

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CN112713266B
CN112713266B CN202011614590.9A CN202011614590A CN112713266B CN 112713266 B CN112713266 B CN 112713266B CN 202011614590 A CN202011614590 A CN 202011614590A CN 112713266 B CN112713266 B CN 112713266B
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negative electrode
active material
electrode active
solid
solid electrolyte
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CN112713266A (en
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李瑞杰
黄海强
王磊
周龙捷
陈少杰
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Svolt Energy Technology Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
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  • Composite Materials (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention discloses a negative electrode slurry and application thereof, wherein the negative electrode slurry comprises: the negative electrode comprises a first negative electrode active material, a second negative electrode active material, a solid electrolyte, conductive carbon and a binder, wherein the lithium intercalation plateau potential of the first negative electrode active material is 0.1V-0.2V, and the lithium intercalation plateau potential of the second negative electrode active material is at least 0.4V higher than the lithium intercalation plateau potential of the first negative electrode active material. By adopting the negative electrode slurry, the diffusion impedance of lithium ions in the negative electrode plate can be reduced on the premise of not increasing the proportion of the conductive agent and the solid electrolyte, the transmission capacity of the lithium ions in the negative electrode plate is improved, and further the multiplying power performance and the quick charging capacity of the battery are improved.

Description

Negative electrode slurry and application thereof
Technical Field
The invention belongs to the technical field of solid-state batteries, and particularly relates to negative electrode slurry and application thereof.
Background
The solid-state battery adopts non-flammable solid-state battery electrolyte to replace flammable organic liquid electrolyte, so that the safety of a battery system is greatly improved, the high-energy anode and cathode can be better adapted, the weight of the system is reduced, and the synchronous improvement of energy density is realized. Among various new battery systems, solid-state batteries are the next-generation technology closest to the industry, which has become a consensus of the industry and the scientific community.
However, the rate performance of the solid-state battery is generally poorer than that of the liquid-state battery, because no liquid is infiltrated in the solid-state battery, the solid particles are connected together only by solid-solid contact, so that the transmission channel of lithium ions is reduced, and because non-lithium ion conductors such as binders are required to be added in the pole piece of the solid-state battery, the transmission of the lithium ions in the pole piece is further restricted.
When the solid-state battery is in a charging state, one side of the negative pole piece, which is close to the electrolyte layer, firstly receives lithium ions transmitted by the positive pole side, but the polarization phenomenon occurs due to the unsmooth conduction of the lithium ions in the negative pole piece, so that the charging performance of the battery is influenced; particularly under a large current, the phenomenon is more obvious, and the quick charging performance of the battery is further influenced.
In order to solve the problems of poor rate performance and high ion transmission impedance in the solid-state battery, one of the methods adopted at present is to increase the proportion of conductive carbon in the positive and negative electrode plates to solve the problem. However, this method has significant drawbacks: (1) the conductive carbon is nano powder particles, is difficult to uniformly disperse in slurry, and is easy to form agglomeration particularly when the content is increased, so that a conductive network cannot be well constructed, and the electronic conductivity is reduced. (2) A solid electrolyte such as a sulfide electrolyte used in a solid battery is unstable at a high voltage, and particularly, it is more likely to undergo a decomposition reaction at a high voltage when it is in contact with conductive carbon, thereby causing a decrease in ion conductivity of the sulfide electrolyte, so that when more conductive carbon is added to positive and negative electrode sheets, it causes rapid deterioration in the contact section of the solid electrolyte with the conductive carbon, and rather, the battery performance is significantly decreased. (3) The increase of the conductive carbon content inevitably occupies the proportion of other substances in the pole piece, and the reduction of the proportion of the active substances in the positive and negative pole pieces can reduce the energy which can be released, thereby causing the reduction of the overall energy density of the battery; meanwhile, the content of the solid electrolyte is reduced, so that an ion conductive network in the cathode coating cannot be well constructed, and the ion conduction limited energy cannot be normally exerted. (4) Although the conductive carbon is a good conductor of electrons, the conductive carbon has a poor transmission effect on lithium ions, and cannot solve the problem of limited lithium ion conduction in the positive and negative electrode plates, so that the fundamental problem of poor rate capability of the solid-state battery cannot be fundamentally solved.
In order to solve the problems of poor rate performance and high ion transmission impedance in the solid-state battery, the second method adopted at present is to increase the proportion of solid electrolyte in positive and negative electrode plates to solve the problem. However, the disadvantages of this method are as follows: (1) the proportion of the solid electrolyte is increased, and the proportion of other substances in the pole piece is inevitably extruded: the reduction of the proportion of active materials in the positive electrode and the negative electrode causes the reduction of the capacity of a pole piece, thereby causing the reduction of the overall energy density of the battery. (2) The cost of the solid electrolyte, especially the sulfide solid electrolyte and the halogen solid electrolyte is very high, and the price of the current solid electrolyte is about 2500 times of that of the positive active material and about 2000 times of that of the negative active material with the same quality, so that the manufacturing cost of the battery can be obviously improved by increasing the proportion of the solid electrolyte in the pole piece of the solid battery.
Therefore, the existing technologies for solving the problems of poor rate performance and high ion transmission impedance in the solid-state battery need to be further researched.
Disclosure of Invention
The present invention is directed to solving, at least to some extent, one of the technical problems in the related art. Therefore, an object of the present invention is to provide a negative electrode paste and an application thereof, by which the diffusion impedance of lithium ions in a negative electrode plate can be reduced and the transmission capability of lithium ions in the negative electrode plate can be improved without increasing the proportion of a conductive agent and a solid electrolyte, so as to improve the rate capability and the quick charging capability of a battery, and compared with a method for increasing the content of the conductive agent or the solid electrolyte, the present invention has the advantages of lower cost and higher energy density of the battery.
In one aspect of the invention, a negative electrode slurry is provided. According to an embodiment of the present invention, the anode paste includes: the lithium-doped lithium ion battery comprises a first negative electrode active material, a second negative electrode active material, a solid electrolyte, conductive carbon and a binder, wherein the lithium intercalation plateau potential of the first negative electrode active material is 0.1V-0.2V, and the lithium intercalation plateau potential of the second negative electrode active material is at least 0.4V higher than the lithium intercalation plateau potential of the first negative electrode active material.
According to the negative electrode slurry provided by the embodiment of the invention, the negative electrode slurry comprises a first negative electrode active material, a second negative electrode active material, a solid electrolyte, conductive carbon and a binder, the lithium intercalation platform potential of the first negative electrode active material is 0.1V-0.2V, the lithium intercalation platform potential of the second negative electrode active material is at least 0.4V higher than that of the first negative electrode active material, the negative electrode plate prepared by applying the negative electrode slurry on a negative electrode current collector is applied to a solid battery, lithium ions transmitted from a positive electrode to the negative electrode plate tend to be preferentially combined with the negative electrode active material with higher lithium intercalation platform potential to form alloy or intercalation, so that the lithium ions in the negative electrode plate are preferentially combined with the second active material with higher lithium intercalation platform potential. Moreover, because the first negative electrode active material and the second negative electrode active material have large potential difference values of lithium intercalation platforms, after the second negative electrode active material preferentially intercalates lithium, a potential difference can be formed between the first negative electrode active material and the second negative electrode active material, and the potential difference can form driving force for lithium ions, so that the transfer of the lithium ions between the first negative electrode active material and the second negative electrode active material can be promoted, and the problems of poor rate capability and large ion transmission impedance in the solid-state battery can be solved. Therefore, compared with the prior art in which a single active material is used as a negative active material, the negative slurry adopted in the application can reduce the diffusion impedance of lithium ions in the negative pole piece and improve the transmission capacity of the lithium ions in the negative pole piece on the premise of not increasing the proportion of the conductive agent and the solid electrolyte, so that the rate capability and the quick charging capability of the battery are improved, and the application has the advantages of lower cost and higher energy density of the battery compared with a method for improving the content of the conductive agent or the solid electrolyte.
In addition, the anode paste according to the above embodiment of the present invention may further have the following additional technical features:
in some embodiments of the present invention, a mass ratio of the first negative electrode active material, the second negative electrode active material, the solid electrolyte, the conductive carbon, and the binder is (20 to 70): (3-18): (0-50): (1-5): (1-5). Therefore, the rate capability and the quick charging capability of the battery can be improved.
In some embodiments of the present invention, the first negative active material includes at least one of graphite, silicon oxide, and silicon.
In some embodiments of the invention, the second negative active material comprises at least one of indium and lithium titanate.
In some embodiments of the present invention, the second anode active material accounts for not more than 25% based on the total mass of the first anode active material and the second anode active material. Therefore, the rate capability and the quick charging capability of the battery can be improved.
In some embodiments of the invention, the solid electrolyte comprises at least one of a sulfide solid electrolyte, an oxide solid electrolyte, and a halogen solid electrolyte.
In some embodiments of the invention, the binder comprises at least one of polyvinylidene fluoride, polyacrylic acid, styrene butadiene rubber, polyamide, polyvinyl alcohol, polyimide, nitrile butadiene rubber, polyethylene imine, and sodium carboxymethylcellulose.
In a second aspect of the invention, a negative electrode plate is provided. According to an embodiment of the present invention, the negative electrode tab includes: a negative current collector; the coating is formed on the negative current collector, and is prepared from the negative slurry. Therefore, the negative pole piece is applied to the solid-state battery, the diffusion impedance of lithium ions in the negative pole piece can be reduced on the premise that the proportion of the conductive agent to the solid-state electrolyte is not increased, the transmission capacity of the lithium ions in the negative pole piece is improved, the multiplying power performance and the quick charging capacity of the battery are further improved, and the negative pole piece has the advantages of lower cost and higher energy density of the battery compared with a method for improving the content of the conductive agent or the solid-state electrolyte.
In a third aspect of the present invention, a solid-state battery is presented. According to an embodiment of the invention, the solid-state battery comprises the negative electrode plate. Therefore, the solid-state battery has the advantages of high rate performance, high quick charging capacity, high energy density and low cost.
In a fourth aspect of the present invention, a vehicle is presented. According to an embodiment of the present invention, the vehicle has the above-described solid-state battery. Therefore, the vehicle loaded with the solid-state battery with high rate performance, high quick charge capacity, high energy density and low cost has excellent cruising ability and power performance, greatly shortens the charge time and reduces the cost.
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Detailed Description
The invention will now be described with reference to specific examples, which are intended to be illustrative only and not to be limiting in any way.
In a first aspect of the invention, a negative electrode slurry is presented. According to an embodiment of the present invention, the anode slurry includes a first anode active material having a lithium intercalation plateau potential of 0.1V to 0.2V, a second anode active material having a lithium intercalation plateau potential at least 0.4V higher than that of the first anode active material, a solid electrolyte, conductive carbon, and a binder.
The inventor finds that by simultaneously adopting two negative electrode active materials, namely a first negative electrode active material and a second negative electrode active material, and adopting the first negative electrode active material with the lithium intercalation plateau potential of 0.1V-0.2V and the second negative electrode active material with the lithium intercalation plateau potential at least 0.4V higher than that of the first negative electrode active material, the negative electrode pole piece prepared by applying the negative electrode slurry on a negative electrode current collector is applied to a solid-state battery, lithium ions transmitted from a positive electrode to the negative electrode pole piece tend to be preferentially combined with the negative electrode active material with higher lithium intercalation plateau potential to form alloy or intercalation, so the lithium ions in the negative electrode pole piece are preferentially combined with the second active material with higher lithium intercalation plateau potential. Moreover, because the first negative electrode active material and the second negative electrode active material have large potential difference values of lithium intercalation platforms, after the second negative electrode active material preferentially intercalates lithium, a potential difference can be formed between the first negative electrode active material and the second negative electrode active material, and the potential difference can form driving force for lithium ions, so that the transfer of the lithium ions between the first negative electrode active material and the second negative electrode active material can be promoted, and the problems of poor rate capability and large ion transmission impedance in the solid-state battery can be solved.
Further, the mass ratio of the first negative electrode active material, the second negative electrode active material, the solid electrolyte, the conductive carbon and the binder is (20-70): (3-18): (0-50): (1-5): (1-5). The inventor finds that if the content of the binder is too low, the strength of the pole piece is low, so that the pole piece cannot be formed or is easy to damage, and if the content of the binder is too high, the internal resistance of the pole piece is increased due to the fact that the binder does not have conductivity, so that the charge-discharge polarization is increased and the battery capacity is reduced; meanwhile, if the content of the conductive carbon is too low, an electronic conductive network in the pole piece is not smooth, the internal resistance of the pole piece is increased, further, the charge-discharge polarization is increased, the battery capacity is reduced, and if the content of the conductive carbon is too high, the conductive carbon occupies the proportion of other active material components, so that the energy density of the battery is reduced, and the content of the conductive carbon with high specific surface area is increased, so that the content of the required binder is increased; in addition, because of the potential difference between the first negative electrode active material and the second negative electrode active material, the potential difference can form a driving force for lithium ions, so that the transmission of the lithium ions between the first negative electrode active material and the second negative electrode active material can be promoted, and if the proportion of the first negative electrode active material is too high and the proportion of the second negative electrode active material is too low, the ionic conduction path caused by the potential driving is too small, the ionic conduction is not smooth, and the purpose of improving the rate capability of the battery cannot be achieved. Therefore, by adopting the mixing proportion, the diffusion impedance of lithium ions in the negative pole piece can be reduced, the transmission capability of the lithium ions in the negative pole piece is improved, and the multiplying power performance and the quick charging capability of the battery are further improved.
Further, the second anode active material accounts for not more than 25% based on the total mass of the first anode active material and the second anode active material. The inventor finds that if the second negative electrode active material accounts for too high, the charge-discharge platform of the second negative electrode active material is higher, the discharge platform voltage of the whole battery is reduced due to the too high content of the second negative electrode active material component, so that the energy density of the battery is reduced, the gram capacity of the second negative electrode active material is obviously lower than that of the first negative electrode active material, and the capacity of the pole piece is obviously reduced due to the too high content of the second negative electrode active material component on the premise that the surface densities are the same. Therefore, the second negative electrode active material with the content can ensure that the battery has higher energy density and capacity. It should be noted that a person skilled in the art can select specific types of the first negative electrode active material and the second negative electrode active material according to actual needs, for example, the first negative electrode active material includes at least one of graphite, silicon oxide, and silicon; the second negative electrode active material includes at least one of indium (intercalation plateau potential of 0.6V) and lithium titanate (intercalation plateau potential of about 1.5V).
In addition, the specific types of the above-mentioned solid electrolyte and binder are not particularly limited, and may be selected by those skilled in the art according to actual needs, for example, the solid electrolyte includes at least one of a sulfide solid electrolyte, an oxide solid electrolyte, and a halogen solid electrolyte; the binder comprises at least one of polyvinylidene fluoride, polyacrylic acid, styrene butadiene rubber, polyamide, polyvinyl alcohol, polyimide, nitrile butadiene rubber, polyethylene imine and sodium hydroxymethyl cellulose.
Therefore, compared with the prior art in which a single active material is used as a negative active material, the negative slurry adopted in the application can reduce the diffusion impedance of lithium ions in the negative pole piece and improve the transmission capacity of the lithium ions in the negative pole piece on the premise of not increasing the proportion of the conductive agent and the solid electrolyte, so that the rate capability and the quick charging capability of the battery are improved, and the application has the advantages of lower cost and higher energy density of the battery compared with a method for improving the content of the conductive agent or the solid electrolyte.
In a second aspect of the invention, a negative electrode plate is provided. According to the embodiment of the invention, the negative pole piece comprises a negative pole current collector and a coating, and the coating is formed on the negative pole current collector, wherein the coating is prepared by adopting the negative pole slurry. Therefore, the negative pole piece is applied to the solid-state battery, the diffusion impedance of lithium ions in the negative pole piece can be reduced on the premise of not increasing the proportion of the conductive agent and the solid-state electrolyte, the transmission capacity of the lithium ions in the negative pole piece is improved, the multiplying power performance and the quick charging capacity of the battery are further improved, and compared with a method for improving the content of the conductive agent or the solid-state electrolyte, the negative pole piece has the advantages of being lower in cost and higher in energy density of the battery. It should be noted that the features and advantages described above for the negative electrode slurry are also applicable to the negative electrode sheet, and are not described herein again.
It should be noted that, a person skilled in the art may select a specific type of the negative electrode current collector according to actual needs, for example, the negative electrode current collector may be a copper foil.
In a third aspect of the present invention, a solid-state battery is presented. According to an embodiment of the invention, the solid-state battery comprises the negative electrode plate. Therefore, the solid-state battery has the advantages of high rate performance, high quick charging capacity, high energy density and low cost. It should be noted that the features and advantages described above for the negative electrode slurry and the negative electrode sheet are also applicable to the solid-state battery, and are not described herein again.
In a fourth aspect of the present invention, a vehicle is presented. According to an embodiment of the present invention, the vehicle has the above-described solid-state battery. Therefore, the vehicle loaded with the solid-state battery with high rate performance, high quick charge capacity, high energy density and low cost has excellent cruising ability and power performance, greatly shortens the charge time and reduces the cost. It should be noted that the features and advantages described above for the solid-state battery are also applicable to the vehicle and will not be described here.
The following embodiments of the present invention are described in detail, and it should be noted that the following embodiments are exemplary only, and are not to be construed as limiting the present invention. In addition, all reagents used in the following examples are commercially available or can be synthesized according to methods herein or known, and are readily available to those skilled in the art for reaction conditions not listed, if not explicitly stated.
Example 1
First negative electrode active material: graphite.
Second negative electrode active material: and (4) indium.
Solid electrolyte: sulfurSolid electrolyte (Li)6PS5Cl)。
Adhesive: polyvinylidene fluoride.
And (3) homogenizing and mixing stage: according to the mass ratio of 53%: 3%: 40%: 2%: mixing the first negative electrode active material, the second negative electrode active material, the solid electrolyte, the binder and the conductive carbon by 2% to obtain negative electrode slurry;
preparing a negative pole piece: and (3) homogenizing the negative electrode slurry, and coating the slurry on a negative current collector copper foil to prepare a negative electrode pole piece.
Assembling the solid-state battery: mixing the negative pole piece with a sulfide electrolyte layer (containing 95 wt% of Li)6PS5Cl and 5 wt% of polyvinylidene fluoride), a positive pole piece (a positive current collector is coated with positive slurry on an aluminum foil, and the positive slurry comprises 60 wt% of lithium cobaltate, 2 wt% of polyvinylidene fluoride, 1 wt% of carbon nano tube and 37 wt% of Li6PS5Cl) were assembled into an all-solid battery, and the all-solid battery was charged to 60% SOC using an ac impedance meter for impedance testing.
Example 2
The mass ratio of the first negative electrode active material, the second negative electrode active material, the solid electrolyte, the binder, and the conductive carbon in example 1 was changed to 48%: 8%: 40%: 2%: 2%, the other conditions were the same as in example 1, and the impedance test was performed using an ac impedance meter to charge the all-solid battery to 60% SOC.
Example 3
The mass ratio of the first negative electrode active material, the second negative electrode active material, the solid electrolyte, the binder, and the conductive carbon in example 1 was changed to 46%: 10%: 40%: 2%: 2%, the other conditions were the same as in example 1, and the impedance test was performed using an ac impedance meter to charge the all-solid battery to 60% SOC.
Example 4
The mass ratio of the first negative electrode active material, the second negative electrode active material, the solid electrolyte, the binder, and the conductive carbon in example 1 was changed to 44%: 12%: 40%: 2%: 2%, the other conditions were the same as in example 1, and the impedance test was performed using an ac impedance meter to charge the all-solid-state battery to 60% SOC.
Example 5
The mass ratio of the first negative electrode active material, the second negative electrode active material, the solid electrolyte, the binder, and the conductive carbon in example 1 was changed to 42%: 14%: 40%: 2%: 2%, the other conditions were the same as in example 1, and the impedance test was performed using an ac impedance meter to charge the all-solid battery to 60% SOC.
Example 6
It is different from example 1 in that the first negative electrode active material is silica, other conditions are the same as example 1, and an impedance test is performed using an ac impedance meter to charge the all-solid battery to 60% SOC.
Example 7
The difference from example 1 is that the first negative electrode active material is silicon, and the oxide solid electrolyte (Li) is used as the solid electrolyte7La3Zr2O12) The electrolyte in the electrolyte layer of the assembled solid-state battery is Li7La3Zr2O12Otherwise, the impedance test was performed using an ac impedance meter to charge the all-solid-state battery to 60% SOC in the same manner as in example 1.
Example 8
The difference from example 1 is that the second negative electrode active material is lithium titanate, and the solid electrolyte is a halogen solid electrolyte (Li)3YCl6) The electrolyte in the electrolyte layer in the assembled solid-state battery is Li3YCl6Otherwise, the impedance test was performed using an ac impedance meter to charge the all-solid-state battery to 60% SOC in the same manner as in example 1.
Comparative example 1
Homogenizing and mixing stage the first negative electrode active material, the solid electrolyte, the binder and the conductive carbon in example 1 were mixed in a mass ratio of 56%: 40%: 2%: 2% hybrid, otherwise as in example 1, and impedance testing was performed using an ac impedance meter to charge the all-solid-state battery to 60% SOC.
Comparative example 2
Homogenizing and mixing stage the second negative electrode active material, the solid electrolyte, the binder and the conductive carbon in example 1 were mixed in a mass ratio of 56%: 40%: 2%: 2% hybrid, otherwise as in example 1, and impedance testing was performed using an ac impedance meter to charge the all-solid-state battery to 60% SOC.
Comparative example 3
Homogenizing and mixing stage the first negative electrode active material, the solid electrolyte, the binder and the conductive carbon in example 6 were mixed in a mass ratio of 56%: 40%: 2%: 2% hybrid, other conditions were the same as in example 6, and the impedance test was performed using an ac impedance meter to charge the all-solid battery to 60% SOC.
Comparative example 4
Homogenizing and mixing stage the first negative electrode active material, the solid electrolyte, the binder, and the conductive carbon in example 7 were mixed in a mass ratio of 56%: 40%: 2%: 2% hybrid, other conditions were the same as in example 7, and the impedance test was performed using an ac impedance meter to charge the all-solid battery to 60% SOC.
Comparative example 5
Homogenizing and mixing stage the first negative electrode active material, the solid electrolyte, the binder and the conductive carbon in example 8 were mixed in a mass ratio of 56%: 40%: 2%: 2% hybrid, other conditions were the same as in example 8, and the impedance test was performed using an ac impedance meter to charge the all-solid battery to 60% SOC.
The impedance test results of examples 1 to 8 and comparative examples 1 to 5 described above and the first cycle charge and discharge efficiency obtained by performing the charge and discharge test are shown in table 1:
TABLE 1 results of impedance test of examples 1 to 8 and comparative examples 1 to 5 and first cycle charge and discharge efficiency obtained by performing charge and discharge test
Figure BDA0002876131520000081
And (4) conclusion: as can be seen from table 1, the all-solid-state battery assembled using the first negative active material alone as the negative active material has a higher resistance value at the same SOC, which is inferior to the resistance value using the second negative active material alone; when a combination of a first negative electrode active material and a second negative electrode active material is used as a negative electrode active material, the all-solid battery has a low resistance value, particularly the lowest resistance value when the mass fraction of the second negative electrode active material is close to 13%; therefore, the mass fraction of the second negative electrode active material is preferably about 13%. The impedance value of the all-solid-state battery composed of different formulas in the same SOC state can reflect the corresponding ion diffusion impedance state, and the lower impedance value reflects that the ion transmission is smoother. Meanwhile, the lower impedance value also enables the ion transmission to consume less energy, so that the overall charge and discharge efficiency of the battery can be improved, and from the charge and discharge efficiency (first cycle) of table 1, it can be seen that examples 1 to 5 have higher first cycle efficiency than comparative examples 1 to 2, example 6 has higher first cycle efficiency than comparative example 3, example 7 has higher first cycle efficiency than comparative example 4, and example 8 has higher first cycle efficiency than comparative example 5.
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.

Claims (7)

1. An anode slurry, comprising: a first negative electrode active material, a second negative electrode active material, a solid electrolyte, conductive carbon, and a binder,
wherein the lithium intercalation plateau potential of the first negative electrode active material is 0.1V to 0.2V, the lithium intercalation plateau potential of the second negative electrode active material is at least 0.4V higher than the lithium intercalation plateau potential of the first negative electrode active material,
the mass ratio of the first negative electrode active material, the second negative electrode active material, the solid electrolyte, the conductive carbon, and the binder is (20-70): (3-18): (40-50): (1-5): (1 to 5) of a solvent,
the first negative electrode active material is graphite, and the second negative electrode active material includes at least one of indium and lithium titanate.
2. The anode slurry according to claim 1, wherein the second anode active material accounts for not more than 25% based on a total mass of the first anode active material and the second anode active material.
3. The anode slurry of claim 1, wherein the solid electrolyte comprises at least one of a sulfide solid electrolyte, an oxide solid electrolyte, and a halogen solid electrolyte.
4. The negative electrode slurry of claim 3, wherein the binder comprises at least one of polyvinylidene fluoride, polyacrylic acid, styrene butadiene rubber, polyamide, polyvinyl alcohol, polyimide, nitrile butadiene rubber, polyethylene imine, and sodium hydroxymethyl cellulose.
5. A negative electrode sheet, comprising:
a negative current collector;
a coating layer formed on the negative electrode current collector, wherein the coating layer is prepared using the negative electrode slurry of any one of claims 1 to 4.
6. A solid-state battery comprising the negative electrode tab of claim 5.
7. A vehicle characterized by comprising the solid-state battery according to claim 6.
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