CN114388798A - Conductive agent, battery positive plate, preparation method and application thereof - Google Patents
Conductive agent, battery positive plate, preparation method and application thereof Download PDFInfo
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- CN114388798A CN114388798A CN202111557019.2A CN202111557019A CN114388798A CN 114388798 A CN114388798 A CN 114388798A CN 202111557019 A CN202111557019 A CN 202111557019A CN 114388798 A CN114388798 A CN 114388798A
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- 239000006258 conductive agent Substances 0.000 title claims abstract description 80
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 33
- 229910021392 nanocarbon Inorganic materials 0.000 claims abstract description 31
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 22
- 239000006229 carbon black Substances 0.000 claims abstract description 18
- 238000005245 sintering Methods 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 6
- 238000003825 pressing Methods 0.000 claims description 20
- 239000002245 particle Substances 0.000 claims description 18
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 12
- 229910052759 nickel Inorganic materials 0.000 claims description 10
- RJEIKIOYHOOKDL-UHFFFAOYSA-N [Li].[La] Chemical compound [Li].[La] RJEIKIOYHOOKDL-UHFFFAOYSA-N 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 239000007774 positive electrode material Substances 0.000 claims description 5
- 230000001681 protective effect Effects 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000007787 solid Substances 0.000 abstract description 25
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 16
- 239000007784 solid electrolyte Substances 0.000 abstract description 12
- 230000005540 biological transmission Effects 0.000 abstract description 7
- 229910052799 carbon Inorganic materials 0.000 abstract description 7
- 125000000524 functional group Chemical group 0.000 abstract description 7
- 238000010438 heat treatment Methods 0.000 abstract description 7
- 239000001301 oxygen Substances 0.000 abstract description 6
- 229910052760 oxygen Inorganic materials 0.000 abstract description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 5
- 230000007547 defect Effects 0.000 abstract description 5
- 239000002253 acid Substances 0.000 abstract description 2
- 229910003481 amorphous carbon Inorganic materials 0.000 abstract description 2
- 239000002077 nanosphere Substances 0.000 abstract description 2
- 238000002156 mixing Methods 0.000 description 25
- 239000000203 mixture Substances 0.000 description 24
- 239000003792 electrolyte Substances 0.000 description 19
- 229910002984 Li7La3Zr2O12 Inorganic materials 0.000 description 17
- 229910001182 Mo alloy Inorganic materials 0.000 description 16
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 14
- 238000001816 cooling Methods 0.000 description 14
- 238000000498 ball milling Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 9
- 229910052744 lithium Inorganic materials 0.000 description 9
- 239000012528 membrane Substances 0.000 description 9
- 229910000846 In alloy Inorganic materials 0.000 description 8
- LHJOPRPDWDXEIY-UHFFFAOYSA-N indium lithium Chemical compound [Li].[In] LHJOPRPDWDXEIY-UHFFFAOYSA-N 0.000 description 8
- 241000872198 Serjania polyphylla Species 0.000 description 7
- 229910052786 argon Inorganic materials 0.000 description 7
- 229910002804 graphite Inorganic materials 0.000 description 6
- 239000010439 graphite Substances 0.000 description 6
- -1 polytetrafluoroethylene Polymers 0.000 description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 description 6
- 230000001976 improved effect Effects 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 229910021393 carbon nanotube Inorganic materials 0.000 description 3
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- 238000012360 testing method Methods 0.000 description 3
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- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
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- 230000000694 effects Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002926 oxygen Chemical class 0.000 description 1
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- 238000001291 vacuum drying Methods 0.000 description 1
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Classifications
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/04—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of carbon-silicon compounds, carbon or silicon
-
- 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
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- 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
- H01M2004/028—Positive 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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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a conductive agent, a battery positive plate, a preparation method and application thereof. A preparation method of a conductive agent comprises the following steps: 1) sintering carbon black to obtain a nano carbon material; 2) and reacting the nano carbon material with nitric acid to obtain the conductive agent. According to the invention, the carbon black is sintered at high temperature to obtain the high-crystallinity carbon nanosphere hybrid, and then the functionalized nitrogen-doped carbon nano conductive agent is obtained by adopting acid heat treatment, so that oxygen-containing functional groups on the surface of the carbon material are eliminated, and simultaneously residual amorphous carbon in the conductive agent is removed, thereby improving an electron transmission channel in the positive plate. The conductive agent has the defect of low surface, and can improve the electronic conductivity of the anode, inhibit the interface reaction between the anode and the solid electrolyte, reduce the internal resistance of the solid battery and prolong the cycle life of the solid battery.
Description
Technical Field
The invention relates to the technical field of batteries, in particular to a conductive agent, a battery positive plate, a preparation method and application thereof.
Background
The all-solid lithium battery can overcome the inherent defects of the traditional liquid lithium ion secondary battery, including electrolyte leakage, flammability and the like, and can obviously improve the energy density of the lithium ion battery, thereby initiating wide interests in the scientific and industrial fields. In order to obtain more excellent electrochemical properties, it is important to balance the ionic conductivity and the electronic conductivity of the solid battery material. In recent years, efforts have been made to develop a solid electrolyte with high ionic conductivity, and a nanocarbon conductive agent can provide a significant positive effect in a solid battery in terms of electron conductivity and improve the electrochemical performance of the battery. However, oxygen-containing functional groups exist on the surface of the conventional carbon conductive agent, and an enough electron seepage path exists in the charging process to accelerate the decomposition of the solid electrolyte, so that the internal interface of the battery is unstable, the internal resistance of the solid battery is increased, and the cycle life of the battery is shortened. Therefore, the whole performance of the solid battery can be greatly improved by introducing a novel stable carbon conductive agent with low surface defect degree to inhibit the interface reaction of the conductive agent/the solid electrolyte.
Patent application No. CN201810506133.4 discloses an all-solid-state battery, which uses a carbon material having a carbonyl group on the surface as a conductive aid to improve the electronic conductivity of the solid-state battery. However, the oxygen-containing carbonyl group on the surface easily causes side reaction at the interface of the solid electrolyte/carbon conductive agent, increases the internal resistance of the battery in the charging and discharging processes, and damages the cycle life of the battery.
Patent application No. CN202010185484.7 discloses a polar carbon nanotube, a method for manufacturing the same, an electrolyte membrane, and a solid battery, in which the conductivity of a solid electrolyte is improved and the interface impedance of the solid battery is reduced by adding the polar carbon nanotube to the solid electrolyte. However, the addition of the carbon nanotube conductive agent to the solid electrolyte does not optimize the conductivity of the positive electrode and the negative electrode, and has certain technical limitations.
Disclosure of Invention
In view of the above-mentioned shortcomings of the prior art, the present invention aims to provide a conductive agent, a battery positive plate, a preparation method and a use thereof, which are used for solving the technical problems in the prior art.
To achieve the above objects and other related objects, the present invention is achieved by the following technical solutions.
The invention provides a preparation method of a conductive agent, which comprises the following steps:
1) sintering carbon black to obtain a nano carbon material;
2) and reacting the nano carbon material with nitric acid to obtain the conductive agent.
Preferably, in step 1), the carbon black has a particle size of 30 to 100 nm.
Preferably, in step 1), the temperature of the sintering is 2000-. In the application, the carbon black is treated at high temperature, so that on one hand, the crystallinity of the nano carbon material is improved, the conductivity and the lithium ion transmission rate are improved, and meanwhile, the oxygen-containing functional groups on the surface can be removed by the high-temperature treatment.
Preferably, in the step 1), the temperature rise rate of the sintering is 5-10 ℃/min.
Preferably, in the step 1), the sintering time is 30-180 min.
Preferably, in step 1), the sintering is performed in a protective atmosphere.
More preferably, the protective atmosphere comprises argon or an inert gas.
Preferably, in step 2), the temperature of the reaction is 120-180 ℃.
Preferably, in step 2), the reaction time is 8-12 h.
Preferably, in the step 2), the molar ratio of the nano carbon material to the nitric acid is (40-55) to (1.5-2.5). In the application, nitric acid is doped into the nano-carbon material as a nitrogen source, and on the other hand, functional groups such as hydroxyl, carboxyl and the like on the surface can be removed, so that the defect density of the nano-carbon material is reduced. The proportion of nitric acid in the application cannot be too low or too high, the nitric acid is not favorable for the nitric acid to play a role, and the proportion is too high, so that the content of nitrogen elements in the nano-carbon material is high, and the conductivity and the transmission performance of lithium ions are reduced.
Preferably, in step 2), the reaction further comprises a post-treatment. The post-treatment comprises cooling, washing and drying.
More preferably, the cooling is to room temperature.
More preferably, the washing is performed using ethanol and water.
Further preferably, the washing is at least three times each with ethanol and water.
More preferably, the temperature of the drying is 25-40 ℃. Further preferably, the drying is performed by a vacuum drying method.
The second object of the present invention is to provide a conductive agent obtained by the above-mentioned method for producing a conductive agent.
The invention also aims to provide the application of the conductive agent in the preparation of the positive plate of the battery.
The invention also aims to provide a battery positive plate which comprises a high-nickel ternary material, lithium lanthanum zirconate and the conductive agent.
Preferably, the high nickel ternary material is selected from one or more of NCM523, NCM622, and NCM 811.
Preferably, the mass ratio of the high-nickel ternary material to the lithium lanthanum zirconate to the conductive agent is (60-80): (10-20): (5-10).
The fifth purpose of the invention is to provide the preparation method of the battery positive plate, which is to mix and press the high-nickel ternary material, the lanthanum lithium zirconate and the conductive agent to obtain the battery positive plate.
Preferably, the mixing is performed using a ball mill. Specifically, the ball milling time is 10-30min, and the ball milling temperature is 20-25 ℃.
Preferably, the pressure at the time of pressing is 30-50 Mpa.
It is a further object of the present invention to provide a solid-state battery including the above-mentioned battery positive electrode material or the above-mentioned conductive agent.
Compared with the prior art, the invention has the following beneficial effects:
1) according to the invention, the high-crystallinity carbon nanosphere hybrid is prepared through high-temperature graphitization, and then the functionalized nitrogen-doped carbon nano conductive agent is obtained through acid heat treatment, so that oxygen-containing functional groups on the surface of the carbon material are eliminated, and simultaneously residual amorphous carbon in the conductive agent is removed, thereby improving an electron transmission channel in the positive plate. The conductive agent has the defect of low surface, and can improve the electronic conductivity of the anode, inhibit the interface reaction between the anode and the solid electrolyte, reduce the internal resistance of the solid battery and prolong the cycle life of the solid battery.
2) The method is simple and is easy for industrial mass production.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
Fig. 1 is a schematic view showing an electron transport path of a positive electrode sheet of comparative example 1 of the present invention.
Fig. 2 is a schematic view showing an electron transport path of a positive electrode sheet according to example 4 of the present invention.
Detailed Description
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention.
Before the present embodiments are further described, it is to be understood that the scope of the invention is not limited to the particular embodiments described below; it is also to be understood that the terminology used in the examples is for the purpose of describing particular embodiments, and is not intended to limit the scope of the present invention; in the description and claims of the present application, the singular forms "a", "an" and "the" include plural referents unless the context clearly dictates otherwise.
When numerical ranges are given in the examples, it is understood that both endpoints of each of the numerical ranges and any value therebetween can be selected unless the invention otherwise indicated. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In addition to the specific methods, devices, and materials used in the examples, any methods, devices, and materials similar or equivalent to those described in the examples may be used in the practice of the invention in addition to the specific methods, devices, and materials used in the examples, in keeping with the knowledge of one skilled in the art and with the description of the invention.
Example 1
In this embodiment, preparing the conductive agent and obtaining the positive plate by using the conductive agent includes:
placing carbon black with the particle size of 30nm in a graphite furnace, sintering at 2200 ℃ for 200min in argon at the heating rate of 7 ℃/min, and cooling to room temperature to obtain the nano carbon material.
And (3) reacting the nano carbon material with nitric acid in a sealed polytetrafluoroethylene lining autoclave at 100 ℃ for 10h, and cooling to room temperature to obtain a conductive agent, wherein the conductive agent is marked as N-NCC. Wherein the molar ratio of the nano carbon material to the nitric acid is 48: 2.
mixing NCM523 and Li7La3Zr2O12And the conductive agent is mixed with the conductive agent according to the mass ratio of 80: 17.5: 2.5 putting the mixture into a high-energy vibration ball mill, ball-milling and mixing for 20min, then transferring the mixture into a molybdenum alloy die, and pressing the mixture under 40Mpa to obtain the positive plate with the thickness of 110 mu m.
Mixing Li7La3Zr2O12Transferring the particles into molybdenum alloy mold, pressing at 35Mpa to obtain film as electrolyte layer with thicknessIs 100 mu; then, a lithium indium alloy negative plate with the thickness of 220 mu m and the lithium percentage of 50 percent and the positive plate are added and respectively pressed on two sides of an electrolyte membrane under 40 standard atmospheric pressures, and the 2032 type button solid battery is assembled.
Example 2
In this embodiment, preparing the conductive agent and obtaining the positive plate by using the conductive agent includes:
placing carbon black with the particle size of 30nm in a graphite furnace, sintering at 2200 ℃ for 200min in argon at the heating rate of 7 ℃/min, and cooling to room temperature to obtain the nano carbon material.
And (3) reacting the nano carbon material with nitric acid in a sealed polytetrafluoroethylene lining autoclave at 100 ℃ for 10h, and cooling to room temperature to obtain a conductive agent, wherein the conductive agent is marked as N-NCC. Wherein the molar ratio of the nano carbon material to the nitric acid is 48: 2.
mixing NCM523 and Li7La3Zr2O12 and the conductive agent in a mass ratio of 80: 16.5: 3.5 putting the mixture into a high-energy vibration ball mill, ball-milling and mixing for 20min, then transferring the mixture into a molybdenum alloy die, and pressing the mixture under 40Mpa to obtain the positive plate with the thickness of 110 mu m.
Mixing Li7La3Zr2O12Transferring the particles into a molybdenum alloy die, pressing under 35Mpa to obtain a film as an electrolyte layer, wherein the thickness of the film is 100 mu; then, a lithium indium alloy negative plate with the thickness of 220 mu m and the lithium percentage of 50 percent and the positive plate are added and respectively pressed on two sides of an electrolyte membrane under 40 standard atmospheric pressures, and the 2032 type button solid battery is assembled.
Example 3
In this embodiment, preparing the conductive agent and obtaining the positive plate by using the conductive agent includes:
placing carbon black with the particle size of 30nm in a graphite furnace, sintering at 2200 ℃ for 200min in argon at the heating rate of 7 ℃/min, and cooling to room temperature to obtain the nano carbon material.
And (3) reacting the nano carbon material with nitric acid in a sealed polytetrafluoroethylene lining autoclave at 100 ℃ for 10h, and cooling to room temperature to obtain a conductive agent, wherein the conductive agent is marked as N-NCC. Wherein the molar ratio of the nano carbon material to the nitric acid is 48: 2.
mixing NCM523 and Li7La3Zr2O12And the conductive agent is mixed with the conductive agent according to the mass ratio of 80: 15: and 5, putting the mixture into a high-energy vibration ball mill, performing ball milling and mixing for 20min, transferring the mixture into a molybdenum alloy mold, and pressing the mixture under 40Mpa to obtain the positive plate with the thickness of 110 microns.
Mixing Li7La3Zr2O12Transferring the particles into a molybdenum alloy die, pressing under 35Mpa to obtain a film as an electrolyte layer, wherein the thickness of the film is 100 mu; then, a lithium indium alloy negative plate with the thickness of 220 mu m and the lithium percentage of 50 percent and the positive plate are added and respectively pressed on two sides of an electrolyte membrane under 30 standard atmospheric pressures, and the 2032 type button solid battery is assembled.
Example 4
In this embodiment, preparing the conductive agent and obtaining the positive plate by using the conductive agent includes:
placing carbon black with the particle size of 60nm in a graphite furnace, sintering at 2200 ℃ for 200min in argon at the heating rate of 7 ℃/min, and cooling to room temperature to obtain the nano carbon material.
And (3) reacting the nano carbon material with nitric acid in a sealed polytetrafluoroethylene lining autoclave at 100 ℃ for 10h, and cooling to room temperature to obtain a conductive agent, wherein the conductive agent is marked as N-NCC. Wherein the molar ratio of the nano carbon material to the nitric acid is 48: 2.
mixing NCM523 and Li7La3Zr2O12And the conductive agent is mixed with the conductive agent according to the mass ratio of 80: 13: 7, putting the mixture into a high-energy vibration ball mill, ball-milling and mixing for 20min, then transferring the mixture into a molybdenum alloy die, and pressing the mixture under 40Mpa to obtain the positive plate with the thickness of 110 mu m.
Mixing Li7La3Zr2O12Transferring the particles into a molybdenum alloy die, pressing under 35Mpa to obtain a film as an electrolyte layer, wherein the thickness of the film is 100 mu; then, a lithium indium alloy negative plate with the thickness of 220 mu m and the lithium percentage of 50 percent and the positive plate are added and respectively pressed on two sides of an electrolyte membrane under 35 standard atmospheric pressures, and the 2032 type button solid battery is assembled.
Example 5
In this embodiment, preparing the conductive agent and obtaining the positive plate by using the conductive agent includes:
placing carbon black with the particle size of 100nm in a graphite furnace, sintering for 180min at the temperature rising rate of 10 ℃/min in argon at the temperature of 2500 ℃, and cooling to room temperature to obtain the nano carbon material.
And (3) reacting the nano carbon material with nitric acid in a sealed polytetrafluoroethylene lining autoclave at 180 ℃ for 12h, and cooling to room temperature to obtain a conductive agent, wherein the conductive agent is marked as N-NCC. Wherein the molar ratio of the nano carbon material to the nitric acid is 55: 1.5.
mixing NCM523 and Li7La3Zr2O12And the conductive agent is mixed with the conductive agent according to the mass ratio of 60: 20: 10, putting the mixture into a high-energy vibration ball mill, ball-milling and mixing for 30min, then transferring the mixture into a molybdenum alloy die, and pressing the mixture under 50Mpa to obtain the positive plate with the thickness of 180 mu m.
Mixing Li7La3Zr2O12Transferring the particles into a molybdenum alloy die, pressing under 40Mpa to obtain a film as an electrolyte layer, wherein the thickness of the film is 150 mu; then adding a lithium indium alloy negative plate with the thickness of 200 mu m and the lithium percentage of 60 percent and the positive plate, respectively pressing the negative plate and the positive plate on two sides of an electrolyte membrane under 40 standard atmospheric pressures, and assembling the 2032 type button solid battery.
Example 6
In this embodiment, preparing the conductive agent and obtaining the positive plate by using the conductive agent includes:
placing carbon black with the particle size of 60nm in a graphite furnace, sintering at 2000 ℃ for 30min in argon at the heating rate of 5 ℃/min, and cooling to room temperature to obtain the nano carbon material.
And (3) reacting the nano carbon material with nitric acid in a sealed polytetrafluoroethylene lining autoclave at 120 ℃ for 8h, and cooling to room temperature to obtain a conductive agent, wherein the conductive agent is marked as N-NCC. Wherein the molar ratio of the nano carbon material to the nitric acid is 40: 2.5.
mixing NCM523 and Li7La3Zr2O12And the conductive agent at a mass ratio of 75: 15: 10, putting the mixture into a high-energy vibration ball mill, ball-milling and mixing for 10min, then transferring the mixture into a molybdenum alloy die, and pressing the mixture under 30Mpa to obtain the positive plate with the thickness of 60 mu m.
Mixing Li7La3Zr2O12Transferring the particles into a molybdenum alloy die, pressing under 30Mpa to obtain a film as an electrolyte layer, wherein the thickness of the film is 50 mu; then adding a lithium indium alloy negative plate with the thickness of 50 mu m and the lithium percentage of 40 percent and the positive plate, respectively pressing the negative plate and the positive plate on two sides of an electrolyte membrane under 35 standard atmospheric pressures, and assembling the 2032 type button solid battery.
Comparative example 1
In this comparative example, the positive electrode sheet did not contain any conductive agent, and the following were included:
mixing NCM523 and Li7La3Zr2O12According to the mass ratio of 80: 20, putting the mixture into a high-energy vibration ball mill, ball-milling and mixing for 20min, then transferring the mixture into a molybdenum alloy mold, and pressing the mixture under 40Mpa to obtain the positive plate with the thickness of 110 mu m.
Mixing Li7La3Zr2O12Transferring the particles into a molybdenum alloy die, pressing under 35Mpa to obtain a film as an electrolyte layer, wherein the thickness of the film is 100 mu; then, a lithium indium alloy negative plate with the thickness of 220 mu m and the lithium percentage of 50 percent and the positive plate are added and respectively pressed on two sides of an electrolyte membrane under 35 standard atmospheric pressures, and the 2032 type button solid battery is assembled.
Comparative example 2
In this comparative example, a positive electrode sheet was prepared using untreated carbon black as a conductive agent, and included the following:
mixing NCM523 and Li7La3Zr2O12And carbon black with the particle size of 60nm according to the mass ratio of 80: 15: and 5, putting the mixture into a high-energy vibration ball mill, performing ball milling and mixing for 20min, transferring the mixture into a molybdenum alloy mold, and pressing the mixture under 40Mpa to obtain the positive plate with the thickness of 110 microns. The untreated carbon black is labeled NC.
Mixing Li7La3Zr2O12Transferring the particles into molybdenum alloy mold, pressing at 35Mpa to obtain film as electrolyte layer with thicknessIs 100 mu; then, a lithium indium alloy negative plate with the thickness of 220 mu m and the lithium percentage of 50 percent and the positive plate are added and respectively pressed on two sides of an electrolyte membrane under 35 standard atmospheric pressures, and the 2032 type button solid battery is assembled.
The solid-state batteries obtained in examples 1 to 4 and comparative examples 1 and 2 were subjected to cycle tests at 60 ℃ in a voltage range of 2.7 to 4.1V and at a charge-discharge rate of 0.1 to 0.2C; and (3) carrying out direct-current internal resistance test on the electrolyte of the solid battery at room temperature by adopting a double-probe method, wherein the direct-current internal resistance mainly reflects the electronic resistivity, and gold is sprayed on the bottom and the top of the sample before the test in order to reduce the measurement error.
TABLE 1 comparison of electrochemical properties of high-nickel composite anodes prepared under different conditions
As can be seen from Table 1, comparative example 2, in which 5% of untreated carbon black was added, had an electron conductivity of 2.3X 10 as compared with comparative example 1, in which no conductive agent was added4The S/cm is increased to 3.2 x 104S/cm, but the cycle life of the solid-state battery decreased from 98 weeks to 76 weeks. The main reasons for this are that untreated carbon black has a low degree of graphitization resulting in low electron conductivity, while the surface contains a series of oxygen-containing functional groups, resulting in Li7La3Zr2O12The solid electrolyte generates side reaction, an insulating layer is formed on the solid electrolyte/NCM interface in the circulation process, the interface impedance of the solid battery is increased, and the cycle life of the battery is shortened.
In example 3, the electron conductivity of the positive electrode sheet was increased to 6.3 x 10 after 5% of the N-NCC conductive agent was added, compared to comparative example 14S/cm, which shows that the high-graphitization conductive agent N-NCC provides an effective electron transmission path for non-direct contact between NCM particles, and the electron transmission path in the positive plate is obviously increased.
After the addition amount of the N-NCC conductive agent exceeds 7%, the performance of the solid battery begins to be reduced, the optimum addition amount is about 5%, an electron transmission path is insufficient due to too low addition amount, and the electric field distribution in the positive plate is uneven due to agglomeration due to too high addition amount.
Fig. 1 is a schematic view of electron transport paths of positive electrode sheets of comparative example and example 3.
As can be seen from fig. 1, functional groups on the surface of the conductive agent can be eliminated through high-temperature sintering and nitric acid hydrothermal treatment, side reactions of the LLZO solid electrolyte are inhibited, the interfacial conductivity and stability are improved, and the actual cycle life of the solid battery is prolonged to 223 weeks.
The invention provides an effective technical approach for improving the electronic conductivity of the nickel composite positive plate and the electrochemical performance of the solid battery, and the method not only can improve the electronic conductivity of the solid battery, but also can prolong the actual cycle life of the battery, and is simple and controllable.
The foregoing embodiments are merely illustrative of the principles and utilities of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which can be made by those skilled in the art without departing from the spirit and technical spirit of the present invention be covered by the claims of the present invention.
Claims (10)
1. A preparation method of a conductive agent is characterized by comprising the following steps:
1) sintering carbon black to obtain a nano carbon material;
2) and reacting the nano carbon material with nitric acid to obtain the conductive agent.
2. The method for producing the conductive agent according to claim 1, wherein in step 1), the particle diameter of the carbon black is 30 to 100 nm;
and/or the sintering temperature is 2000-2500 ℃;
and/or, the sintering is carried out in a protective atmosphere;
and/or the sintering time is 30-180 min.
3. The method for preparing the conductive agent as claimed in claim 1, wherein the temperature of the reaction in step 2) is 120-180 ℃;
and/or the reaction time is 8-12 h;
and/or the molar ratio of the nano carbon material to the nitric acid is (40-55) to (1.5-2.5).
4. The conductive agent obtained by the method for producing a conductive agent according to any one of claims 1 to 3.
5. Use of the conductive agent according to claim 4 for producing a positive electrode sheet for a battery.
6. A positive electrode sheet for a battery comprising a high nickel ternary material, lanthanum lithium zirconate and the conductive agent as defined in claim 4.
7. The positive electrode sheet for batteries according to claim 6, wherein said high nickel ternary material is selected from one or more of NCM523, NCM622 and NCM 811;
and/or the mass ratio of the high-nickel ternary material, the lithium lanthanum zirconate and the conductive agent is (60-80): (10-20): (5-10).
8. The method for preparing a positive electrode material for a battery according to claim 6 or 7, wherein a high nickel ternary material, lanthanum lithium zirconate and the conductive agent are mixed and pressed to obtain the positive electrode material for a battery.
9. The method for producing a battery positive electrode material according to claim 6 or 7, characterized in that the pressure at the time of pressing is 30 to 50 Mpa.
10. A solid-state battery comprising the battery positive electrode material according to claim 6 or 7 or the conductive agent according to claim 4.
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