CN116936816A - Skeleton composite material, preparation method thereof, negative plate and battery - Google Patents
Skeleton composite material, preparation method thereof, negative plate and battery Download PDFInfo
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- CN116936816A CN116936816A CN202311204576.5A CN202311204576A CN116936816A CN 116936816 A CN116936816 A CN 116936816A CN 202311204576 A CN202311204576 A CN 202311204576A CN 116936816 A CN116936816 A CN 116936816A
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- 239000002131 composite material Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title abstract description 17
- 239000004005 microsphere Substances 0.000 claims abstract description 84
- 229920000642 polymer Polymers 0.000 claims abstract description 46
- 229910052751 metal Inorganic materials 0.000 claims abstract description 39
- 239000002184 metal Substances 0.000 claims abstract description 39
- 238000000034 method Methods 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 239000006258 conductive agent Substances 0.000 claims description 49
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 24
- 238000006116 polymerization reaction Methods 0.000 claims description 24
- 239000002994 raw material Substances 0.000 claims description 14
- 239000003054 catalyst Substances 0.000 claims description 13
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 12
- 239000004202 carbamide Substances 0.000 claims description 10
- 239000011248 coating agent Substances 0.000 claims description 10
- 238000000576 coating method Methods 0.000 claims description 10
- 239000011159 matrix material Substances 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 7
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 claims description 6
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- 101000806914 Homo sapiens AP-2 complex subunit sigma Proteins 0.000 claims description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 4
- JPYHHZQJCSQRJY-UHFFFAOYSA-N Phloroglucinol Natural products CCC=CCC=CCC=CCC=CCCCCC(=O)C1=C(O)C=C(O)C=C1O JPYHHZQJCSQRJY-UHFFFAOYSA-N 0.000 claims description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 4
- -1 aralkyl phenol Chemical compound 0.000 claims description 4
- 229910021389 graphene Inorganic materials 0.000 claims description 4
- 239000002105 nanoparticle Substances 0.000 claims description 4
- QCDYQQDYXPDABM-UHFFFAOYSA-N phloroglucinol Chemical compound OC1=CC(O)=CC(O)=C1 QCDYQQDYXPDABM-UHFFFAOYSA-N 0.000 claims description 4
- 229960001553 phloroglucinol Drugs 0.000 claims description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 4
- 125000002256 xylenyl group Chemical class C1(C(C=CC=C1)C)(C)* 0.000 claims description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 3
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- 235000019253 formic acid Nutrition 0.000 claims description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 claims description 2
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 2
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 claims description 2
- 229920000877 Melamine resin Polymers 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 2
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 claims description 2
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 claims description 2
- 229940092714 benzenesulfonic acid Drugs 0.000 claims description 2
- 239000004917 carbon fiber Substances 0.000 claims description 2
- 229930003836 cresol Natural products 0.000 claims description 2
- 235000011167 hydrochloric acid Nutrition 0.000 claims description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 2
- 239000002082 metal nanoparticle Substances 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 2
- 239000002070 nanowire Substances 0.000 claims description 2
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- KJOMYNHMBRNCNY-UHFFFAOYSA-N pentane-1,1-diamine Chemical compound CCCCC(N)N KJOMYNHMBRNCNY-UHFFFAOYSA-N 0.000 claims description 2
- 239000001294 propane Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 229910052744 lithium Inorganic materials 0.000 abstract description 88
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 72
- 239000000463 material Substances 0.000 abstract description 19
- 239000003792 electrolyte Substances 0.000 abstract description 15
- 239000011148 porous material Substances 0.000 abstract description 8
- 230000008569 process Effects 0.000 abstract description 5
- 230000010287 polarization Effects 0.000 abstract description 3
- 239000010405 anode material Substances 0.000 abstract description 2
- 239000010406 cathode material Substances 0.000 abstract description 2
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- 238000005530 etching Methods 0.000 description 9
- 239000002245 particle Substances 0.000 description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 7
- 239000011889 copper foil Substances 0.000 description 7
- 238000001878 scanning electron micrograph Methods 0.000 description 7
- 238000010998 test method Methods 0.000 description 7
- 230000001276 controlling effect Effects 0.000 description 6
- 239000011888 foil Substances 0.000 description 6
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 5
- 239000011230 binding agent Substances 0.000 description 5
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 description 5
- 238000007599 discharging Methods 0.000 description 5
- 239000008098 formaldehyde solution Substances 0.000 description 5
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- 239000004094 surface-active agent Substances 0.000 description 5
- 229910013870 LiPF 6 Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 239000007773 negative electrode material Substances 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 2
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- 238000005096 rolling process Methods 0.000 description 2
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
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- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
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- 238000009831 deintercalation Methods 0.000 description 1
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- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
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- 238000010907 mechanical stirring Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
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Classifications
-
- 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
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/665—Composites
-
- 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
-
- 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
- H01M4/134—Electrodes based on metals, Si or alloys
-
- 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
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/668—Composites of electroconductive material and synthetic resins
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Composite Materials (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The application provides a skeleton composite material and a preparation method thereof, a negative plate and a battery, and relates to the technical field of new energy. The skeleton composite material is of a porous polymer microsphere structure, and regulates and controls the conductivity of the polymer microsphere, so that the conductivity of the inner core of the skeleton composite material is higher than that of the outer layer, metal lithium is induced to be deposited in the polymer microsphere preferentially, the pores of the microsphere are fully utilized, and the volume expansion in circulation is avoided; meanwhile, the contact between the metal lithium and the electrolyte is reduced, the side reaction is reduced, and the cycle performance of the metal lithium anode material is greatly improved. The polymer microsphere has no reactivity with metal lithium, the non-conductive characteristic reduces SEI generated in the circulation process, the coulomb efficiency in the circulation of the cathode material is improved, and the service life of the battery is prolonged. The material has a porous structure, and can improve the wettability of electrolyte; the higher specific surface area can provide more reaction sites, so that the charge and discharge efficiency of the battery under high current is enhanced, and the polarization is reduced.
Description
Technical Field
The application relates to the technical field of new energy, in particular to a skeleton composite material and a preparation method thereof, a negative plate and a battery.
Background
Along with the development of lithium ion battery technology, a lithium ion battery system which takes lithium iron phosphate and ternary materials as an anode and takes artificial graphite and natural graphite as a cathode is formed, but the energy density can only reach 300wh/kg at most, and the breakthrough of 350wh/kg is difficult to continue to be improved. Lithium metal is considered the final negative electrode material for high density electrochemical energy storage technology due to its ultra-high specific capacity (3860 mAh/g), lowest redox potential (-3.04V (vs. she)). In addition, since lithium metal negative electrodes themselves contain lithium, many positive electrodes that do not contain lithium, such as sulfur, oxygen, etc., can be used, enabling lithium metal batteries to achieve higher energy densities (> 500 Wh/kg).
However, the development of metallic lithium negative electrodes has not been widely used so far, and many problems remain to be solved. On the one hand, lithium dendrites are easy to generate due to uneven deposition of lithium ions on the surface of metal lithium, so that the positive electrode and the negative electrode are short-circuited due to the fact that the separator is pierced. In addition, lithium dendrites have poor mechanical stability and may be separated from the metallic lithium matrix during cycling, forming "dead lithium" which results in loss of electrochemically active lithium and affects cycling efficiency. On the other hand, due to the volume expansion effect of the metal lithium, the generated stress causes continuous rupture and regeneration of the SEI film on the surface of the electrode, and the metal lithium is in direct contact with the electrolyte, so that the electrolyte and the metal lithium in the battery are continuously consumed, meanwhile, the structure of the negative electrode is unstable, and the cycle performance is further reduced.
The existing lithium metal negative electrode is mainly divided into a plurality of categories such as directly adopting metal lithium foil, three-dimensional current collector to load lithium, lithium metal and other elements to prepare alloy composite materials, and the three-dimensional current collector and the composite materials have potential in order to avoid volume change and continuous rupture/generation of SEI films in the circulation process from the practical application point of view.
Three-dimensional current collection is embodied by mainly adopting a metal base, a carbon base and an organic base. The high porosity of the three-dimensional current collector can provide a larger lithium storage space, relieve the volume expansion effect in the process of depositing/dissolving metallic lithium, reduce the generation of lithium dendrites and inhibit the growth of the lithium dendrites. However, for the metal-based current collector, the energy density of the anode can be greatly reduced because of the higher density of the metal base, and the advantage of high energy density brought by the metal lithium anode is weakened. Although the density of the carbon-based material is smaller, the carbon material is generally electrochemically active, lithium intercalation and deintercalation can occur in the circulation, SEI can be formed, the circulation coulomb efficiency of the lithium metal cathode is reduced, and the service life of the battery is influenced. The general organic matrix material is a membranous porous current collector material, and the conductive agent and the conductive ion material added in the modification process of the membranous porous current collector material are not only distributed in the pore canal of the current collector, but also distributed on the surface of the organic matrix film, so that metal lithium can be deposited in the pore and also deposited on the surface, and the surface metal lithium and electrolyte can continuously react to generate dead lithium and dendrite, thereby influencing the cycle life of the battery.
Disclosure of Invention
The application aims to provide a framework composite material, a preparation method thereof, a negative plate and a battery, so as to solve the problems.
In order to achieve the above purpose, the application adopts the following technical scheme:
the application firstly provides a skeleton composite material, the structural schematic diagram of which is shown in figure 1, wherein the skeleton composite material is porous polymer microspheres, conductive agents are distributed in holes of the porous polymer microspheres, the porous polymer microspheres comprise a high-conductivity inner core and a low-conductivity outer layer coating the high-conductivity inner core, and the conductive agents distributed in the holes of the high-conductivity inner core are higher than the conductive agents distributed in the holes of the low-conductivity outer layer.
In one embodiment, the mass ratio of the conductive agent element in the porous polymer microsphere is M1, and the mass ratio of the conductive agent element in the highly conductive core is M2, wherein M1 and M2 satisfy: m1+2% < M2, and M1 and M2 are both in the range of 1% -10%.
In one embodiment, the porous polymeric microsphere has a conductivity of σ1 and the highly conductive core has a conductivity of σ2, wherein σ1 and σ2 satisfy: sigma 1+0.1S/cm < Sigma 2, and both Sigma 1 and Sigma 2 are greater than 0.1S/cm.
In one embodiment, the porous polymeric microspheres have a D50 of 2 to 100 μm.
Preferably, the porous polymeric microspheres satisfy at least one of the following conditions:
A. the specific surface area of the porous polymer microsphere is 20-1000 m 2 /g；
B. The true density of the porous polymer microsphere is 1-1.7 g/cm 3 ；
C. The tap density of the porous polymer microsphere is 0.15-0.36 g/cm 3 ；
D. The compaction density of the porous polymer microsphere is 0.7-1.2 g/cm 3 ；
E. The porosity of the porous polymer microsphere is 10% -95%;
F. the porosity of the porous polymer microsphere is 60% -90%.
The application also provides a preparation method of the framework composite material, which comprises the following steps:
adding a first conductive agent and a first catalyst into a first polymerization raw material solution, and performing a first polymerization reaction to obtain high-conductivity core microspheres;
adding the high-conductivity inner core microsphere into a second polymerization raw material solution, adding a second conductive agent and a second catalyst, and performing a second polymerization reaction on the surface of the high-conductivity inner core microsphere to form a low-conductivity outer layer, so as to obtain a skeleton composite material with a porous polymer microsphere structure;
wherein the mass concentration C1 of the first conductive agent in the first polymerization raw material solution is higher than the mass concentration C2 of the second conductive agent in the second polymerization raw material solution, and C1 > C2+1.
Preferably, the preparation method satisfies at least one of the following conditions:
a. the first polymerization raw material solution and the second polymerization raw material solution are respectively and independently selected from one or more of resorcinol, phenol, xylenol, urea, formaldehyde, phloroglucinol, cresol, nonylphenol, xylenol, melamine, decaphenol propane, aralkyl phenol, furfuryl alcohol, acrylic acid, phthalic acid, pentanediamine, ethylene, propylene, chloroethylene, acrylonitrile, methacrylic acid, acetaldehyde and vinyl alcohol;
b. the first conductive agent and the second conductive agent are respectively and independently selected from one or a combination of at least two of metal nanowires, metal nanoparticles, conductive carbon black, carbon nanotubes, carbon fibers, graphene nanoparticles and graphene oxide nanoparticles;
c. the mass concentration of the first conductive agent and the second conductive agent is respectively and independently 1-20 g/L;
d. the first catalyst and the second catalyst are respectively and independently selected from any one of formic acid, hydrochloric acid, oxalic acid and benzenesulfonic acid;
e. the first catalyst and the second catalyst respectively regulate the pH value of the reaction solution to be less than 5.
Preferably, the preparation method satisfies at least one of the following conditions:
(1) The temperature of the first polymerization reaction is 20-90 ℃, and the temperature of the second polymerization reaction is 20-90 ℃;
(2) The time of the first polymerization reaction is 0.5-10 h, and the time of the second polymerization reaction is 1-5 h.
The application also provides a negative plate, which comprises the framework composite material.
The application also provides a battery, which comprises the negative plate.
Compared with the prior art, the application has the beneficial effects that:
the skeleton composite material provided by the application is of a porous polymer microsphere structure, and the conductivity of the polymer microsphere is regulated and controlled through structural design, so that the conductivity of the inner core of the skeleton composite material is higher than that of the outer layer, metal lithium is induced to be deposited in the polymer microsphere preferentially, the pores of the microsphere are fully utilized, and the volume expansion in circulation is avoided; meanwhile, the contact between the metal lithium and the electrolyte is reduced, the side reaction is reduced, and the cycle performance of the metal lithium anode material is greatly improved. The polymer microsphere has no reactivity with metal lithium, the non-conductive characteristic reduces SEI generated in the circulation process, the coulomb efficiency in the circulation of the cathode material is improved, and the service life of the battery is prolonged. The material has a porous structure, and can improve the wettability of electrolyte; the higher specific surface area can provide more reaction sites, so that the charge and discharge efficiency of the battery under high current is enhanced, and the polarization is reduced. The high molecular material used by the material has low density, and the prepared lithium metal anode has the advantage of high energy density, and the synthesis method is simple and has low cost.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are needed in the embodiments will be briefly described below, it being understood that the following drawings only illustrate some embodiments of the present application and therefore should not be considered as limiting the scope of the present application.
FIG. 1 is a schematic structural view of a skeletal composite material of the present application;
FIG. 2 is a surface SEM image of porous polymeric microspheres prepared in example 1;
FIG. 3 is a sectional SEM image of the porous polymeric microspheres prepared in example 1;
FIG. 4 is an SEM image before depositing metallic lithium of the porous polymeric microspheres prepared in example 1;
FIG. 5 is an SEM image of the porous polymeric microspheres prepared in example 1 after deposition of metallic lithium;
FIG. 6A is a graph showing the TG test curves before etching the porous polymer microspheres prepared in example 6;
FIG. 6B is a graph showing the TG test after etching the porous polymer microspheres prepared in example 6;
FIG. 7 is an SEM image of the surface of a pole piece after deposition of metallic lithium with the material of comparative example 1;
FIG. 8 is an SEM image of the surface of a pole piece after deposition of metallic lithium with the material of example 1;
fig. 9 is a graph of the performance results of the full cell of example 3;
fig. 10 is a graph of the performance results of the full cell of comparative example 4.
Detailed Description
The term as used herein:
"prepared from … …" is synonymous with "comprising". The terms "comprising," "including," "having," "containing," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, step, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, step, method, article, or apparatus.
The conjunction "consisting of … …" excludes any unspecified element, step or component. If used in a claim, such phrase will cause the claim to be closed, such that it does not include materials other than those described, except for conventional impurities associated therewith. When the phrase "consisting of … …" appears in a clause of the claim body, rather than immediately following the subject, it is limited to only the elements described in that clause; other elements are not excluded from the stated claims as a whole.
When an equivalent, concentration, or other value or parameter is expressed as a range, preferred range, or a range bounded by a list of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when ranges of "1 to 5" are disclosed, the described ranges should be construed to include ranges of "1 to 4", "1 to 3", "1 to 2 and 4 to 5", "1 to 3 and 5", and the like. When a numerical range is described herein, unless otherwise indicated, the range is intended to include its endpoints and all integers and fractions within the range.
In these examples, the parts and percentages are by mass unless otherwise indicated.
"parts by mass" means a basic unit of measurement showing the mass ratio of a plurality of components, and 1 part may be any unit mass, for example, 1g may be expressed, 2.689g may be expressed, and the like. If we say that the mass part of the a component is a part and the mass part of the B component is B part, the ratio a of the mass of the a component to the mass of the B component is represented as: b. alternatively, the mass of the A component is aK, and the mass of the B component is bK (K is an arbitrary number and represents a multiple factor). It is not misunderstood that the sum of the parts by mass of all the components is not limited to 100 parts, unlike the parts by mass.
"and/or" is used to indicate that one or both of the illustrated cases may occur, e.g., a and/or B include (a and B) and (a or B).
Embodiments of the present application will be described in detail below with reference to specific examples, but it will be understood by those skilled in the art that the following examples are only for illustrating the present application and should not be construed as limiting the scope of the present application. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The test methods used in the following examples and comparative examples are as follows:
the content of the conductive agent of the porous polymer microsphere particles is tested by TG, and the element content of the overall conductive agent of the particles is measured firstly; then, the outer layer of the resin particles is etched by a resin etching liquid in a liquid phase, and the etching depth (20%r etching depth) is controlled by controlling the time; and then the content of the conductive agent in the high-conductivity core is measured by TG.
The material particle size range was tested by a malvern laser particle size tester MS 2000 and the average particle size of the feedstock particles.
The specific surface area of the material was tested by a Tristar3000 fully automatic specific surface area and porosity analyzer from microphone instruments, usa.
The true density of the material was tested by gas-volumetric methods.
The tap density of the material was measured by a tap density analyzer.
The compacted density of the material was tested by an automated compaction densitometer.
Porosity was measured by a microphone company high performance fully automatic mercury porosimeter AutoPore IV 9500.
Example 1
A preparation method of a framework composite material comprises the following steps:
(1) 2L of water was added to a beaker of 5L, followed by 200 g of urea and super-P at a concentration of 4 g/L, and 160 g of formaldehyde solution was added with stirring; and adding 4 g hydrochloric acid to regulate the pH of the solution to be less than 5, controlling the reaction temperature to be 30 ℃ in a water bath, carrying out suction filtration washing after 2 h, taking out the solution when the pH reaches about 7, and drying the solution in an oven at 80 ℃ to obtain dry gray powder substances, thus obtaining the high-conductivity inner core microsphere, wherein the conductivity of the conductive inner core microsphere is 0.3691S/cm through a powder conductivity test.
(2) Adding 5g of the high-conductivity core microsphere into 100 mL of 0.5 mol/L formaldehyde, adding 0.05g of cetyltrimethylammonium chloride as a surfactant, soaking 2 h, performing suction filtration, adding a suction filtration product into 100 mL of 3mol/L urea and super-P mixed solution with the concentration of 1g/L, stirring, adding hydrochloric acid to adjust the pH to about 2, reacting for 2 h, performing suction filtration and washing to be neutral, and finally washing and drying to obtain porous polymer microsphere with layered distribution of the conductive agent, wherein the surface SEM (scanning electron microscope) graph is shown in FIG. 2, the particle size of the porous polymer microsphere is 10-20 mu m, the SEM graph is shown in FIG. 3, abundant pore structures can be seen from the sectional graph, lithium metal deposition can be contained, and the conductive agent particles are distributed in the pores, so that the conductive agent can enter the microsphere to play the role of conductive deposition sites by an in-situ compounding method, the conductive deposition of metal lithium is induced, and the porous polymer microsphere is measured to be 0.1312S/cm by a powder conductivity test.
Preparing a lithium battery:
button type half cell: coating the obtained skeleton composite material on copper foil with binder LA133 alone, slicing, and assembling half cell with metal lithium foil with electrolyte of 1.0M LiPF 6 in EC:DMC:EMC＝1:1:1Vol％。
Deposition at 0.1C of 4mAh/cm 2 SEM images of the metal lithium before and after the metal lithium is deposited on the framework composite material are respectively shown in FIG. 4 and FIG. 5, and the metal lithium is deposited at the speed of 4mAh/cm 2 After the metallic lithium, the surface of the polymer was substantially free of metallic lithium deposition, which means that metallic lithium was preferentially deposited internally by the polymer and tested for pole piece expansion.
Discharging at 0.1C, depositing 4mAh/cm 2 Metallic lithium, then charged to 1.5V, and its first week coulomb was testedEfficiency is improved.
Example 2
A preparation method of a framework composite material comprises the following steps:
(1) 2L of water was added to a beaker of 5L, followed by 300 g of phloroglucinol and super-P at a concentration of 4 g/L, and 160 g of formaldehyde solution was added with stirring; and adding 4 g hydrochloric acid to regulate the pH of the solution to be less than 5, controlling the reaction temperature to be 40 ℃ in a water bath, carrying out suction filtration washing after 2 h, taking out the solution when the pH reaches about 7, and drying the solution in an oven at 80 ℃ to obtain dry gray powder, thus obtaining the high-conductivity inner core microsphere, wherein the conductivity of the conductive inner core microsphere is 0.4230S/cm through a powder conductivity test.
(2) Adding 5g of the high-conductivity core microsphere into 100 mL of 0.5 mol/L formaldehyde, adding 0.05g of cetyltrimethylammonium chloride as a surfactant, soaking for 2 h, performing suction filtration, adding the suction filtration product into 100 mL of mixed solution of 3mol/L phloroglucinol and super-P with the concentration of 1g/L, stirring, adding hydrochloric acid to adjust the pH to about 2, reacting for 2 h, performing suction filtration and washing to be neutral, and finally washing and drying to obtain porous polymer microsphere with layered distribution of the conductive agent, wherein the conductivity is 0.1632S/cm through a powder conductivity test.
Preparing a lithium battery:
and (3) coating the obtained skeleton composite material on a copper foil by adding a binder LA133, slicing and assembling the half cell with a metal lithium foil, wherein the electrolyte is 1.0M LiPF6 in EC:DMC:EMC =1:1:1 vol%.
Deposition at 0.1C of 4mAh/cm 2 And testing the expansion rate of the pole piece by using metal lithium.
Discharging at 0.1C, depositing 4mAh/cm 2 Metallic lithium was then charged to 1.5V and tested for first week coulombic efficiency.
Example 3
The skeleton composite material prepared in the example 1 is taken as a negative electrode material, and the assembled full battery is prepared by the following specific steps:
(1) Coating the obtained skeleton composite material on copper foil by only adding an adhesive LA133, and drying;
(2) Compounding the lithium metal pole piece with metal lithium through mechanical rolling;
(3) The whole cell was sliced and assembled with lithium iron phosphate.
Example 4
The preparation method and the test method are the same as those of example 1, except that: the conductive agent used in example 4 was carbon nanotubes.
Example 5
The preparation method and the test method are the same as those of example 1, except that: the conductive agent used in example 5 was ketjen black.
Example 6
The preparation method and the test method are the same as those of example 1, except that: the conductive agent used in example 6 was Ag nanowires.
Fig. 6A is a TG test curve before etching of the porous polymeric microspheres of example 6, and fig. 6B is a TG test curve after etching of the porous polymeric microspheres of example 6, from which it can be determined that the content M1 of the Ag element of the conductive agent in the porous polymeric microspheres is 4.7% before etching and the content M2 of the Ag element of the conductive agent in the highly conductive core is 7.8% after etching.
Example 7
The preparation method, raw materials and test method were the same as in example 1 except that: in the first step of synthesis of the highly conductive core microsphere in example 7, super-P was used at a concentration of 5 g/L as a conductive agent; the second step of preparing and synthesizing the low-conductivity outer layer uses super-P with the concentration of the conductive agent of 0.5 g/L.
Example 8
The preparation method and the test method are the same as those of example 1, except that: the acidic catalyst used in example 8 was formic acid.
Example 9
The preparation method and the test method are the same as those of example 2, except that: the starting material for the polymerized monomer used in example 9 was resorcinol.
Comparative example 1
Comparative example 1 a matrix composite material with consistent inner and outer layers of conductive agent content was prepared as follows:
(1) Firstly adding 2L of water into a beaker of 5L, then adding 200 g of urea and super-P with the concentration of 4 g/L, and adding 160 g of formaldehyde solution under stirring; and adding 4 g hydrochloric acid to regulate the pH of the solution to be less than 5, controlling the reaction temperature to be 30 ℃ in a water bath, carrying out suction filtration washing after 2 h, taking out the solution when the pH reaches about 7, and drying the solution in an oven at 80 ℃ to obtain a dry gray powder substance, thus obtaining the high-conductivity inner core microsphere, wherein the conductivity of the high-conductivity inner core microsphere is 0.3725S/cm through a powder conductivity test.
(2) Adding 5g of the high-conductivity core microsphere into 100 mL of 0.5 mol/L formaldehyde, adding 0.05g of cetyltrimethylammonium chloride as a surfactant, soaking for 2 h, performing suction filtration, adding the suction filtration product into 100 mL of 3mol/L urea and super-P mixed solution with the concentration of 4 g/L, stirring, adding hydrochloric acid to adjust the pH to about 2, reacting for 2 h, performing suction filtration and washing to be neutral, and finally washing and drying to obtain the high-molecular microsphere with consistent content of the inner layer and the outer layer of the conductive agent, wherein the conductivity is 0.3925S/cm through a powder conductivity test.
Preparing a lithium battery:
button type half cell: coating the obtained skeleton composite material on copper foil with binder LA133 alone, slicing, and assembling half cell with metal lithium foil with electrolyte of 1.0M LiPF 6 in EC:DMC:EMC＝1:1:1Vol％。
Deposition at 0.1C of 4mAh/cm 2 And testing the expansion rate of the pole piece by using metal lithium.
Discharging at 0.1C, depositing 4mAh/cm 2 Metallic lithium was then charged to 1.5V and tested for first week coulombic efficiency.
Comparative example 2
Comparative example 2 a matrix composite material having a lower conductive agent content in the inner layer than in the outer layer was prepared as follows:
(1) Firstly adding 2L of water into a beaker of 5L, then adding 200 g of urea and super-P with the concentration of 1g/L, and adding 160 g of formaldehyde solution under stirring; and adding 4 g hydrochloric acid to regulate the pH of the solution to be less than 5, controlling the reaction temperature to be 30 ℃ in a water bath, performing suction filtration and washing after a period of time, taking out the solution when the pH reaches about 7, and drying the solution in an oven at 80 ℃ to obtain dry gray powder substances, thereby obtaining the low-conductivity core microsphere, wherein the conductivity of the low-conductivity core microsphere is 0.1027S/cm through a powder conductivity test.
(2) Adding 5g of the low-conductivity polymer core microsphere into 100 mL of 0.5 mol/L formaldehyde, adding 0.05g of cetyltrimethylammonium chloride as a surfactant, soaking for 2 h, performing suction filtration, adding a suction filtration product into 100 mL of 3mol/L urea and super-P mixed solution with the concentration of 4 g/L, stirring, adding hydrochloric acid to adjust the pH to about 2, reacting for 2 h, performing suction filtration and washing to be neutral, and finally washing and drying to obtain the polymer microsphere with layered distribution of the conductive agent, wherein the conductivity of the polymer microsphere is 0.3844S/cm through a powder conductivity test.
Button type half cell: coating the obtained skeleton composite material on copper foil with binder LA133 alone, slicing, and assembling half cell with metal lithium foil with electrolyte of 1.0M LiPF 6 in EC:DMC:EMC＝1:1:1Vol％。
Deposition at 0.1C of 4mAh/cm 2 And testing the expansion rate of the pole piece by using metal lithium.
Discharging at 0.1C, depositing 4mAh/cm 2 Metallic lithium was then charged to 1.5V and tested for first week coulombic efficiency.
Comparative example 3
A preparation method of a framework composite material comprises the following steps:
(1) Firstly, adding 2L of water into a beaker of 5L, then adding 200 g of urea, using mechanical stirring, waiting for uniform dispersion of monomers, then adding 160 g of formaldehyde solution, stirring, and stopping stirring after stirring for 5 min; and adding 4 g hydrochloric acid to regulate the pH of the solution to be less than 3, controlling the reaction temperature to be 30 ℃ in a water bath, carrying out suction filtration washing after 2 h, taking out the solution when the pH reaches about 7, and drying the solution in an oven at 80 ℃ to obtain a dry white powder substance, thus obtaining the polymer core microsphere.
(2) Adding 5g of the polymer core microsphere into 100 mL of 0.5 mol/L formaldehyde, adding 0.05g of cetyltrimethylammonium chloride as a surfactant, soaking for 2 h, performing suction filtration, adding the suction filtration product into 100 mL of 3mol/L urea solution, stirring, adding hydrochloric acid to adjust the pH to about 2, reacting for 2 h, performing suction filtration, washing to be neutral, and finally washing and drying to obtain the porous polymer microsphere of comparative example 3.
The skeleton composite material does not contain conductive substances, and a conductive agent needs to be added during coating.
Preparing a lithium battery:
button type half cell: coating the obtained skeleton material with conductive agent and binder LA133 on copper foil, slicing, and assembling half cell with metal lithium foil with electrolyte of 1.0M LiPF 6 in EC:DMC:EMC＝1:1:1Vol％。
Deposition at 0.1C of 4mAh/cm 2 And testing the expansion rate of the pole piece by using metal lithium.
Discharging at 0.1C, depositing 4mAh/cm 2 Metallic lithium was then charged to 1.5V and tested for first week coulombic efficiency.
Comparative example 4
The skeleton composite material obtained in comparative example 1 is used as a negative electrode material to prepare an assembled full battery, and the specific steps are as follows:
(1) Coating the obtained skeleton composite material with a conductive agent and an adhesive LA133 on a copper foil, and drying;
(2) Compounding the lithium metal pole piece with metal lithium through mechanical rolling;
(3) The whole cell was sliced and assembled with lithium iron phosphate.
Table 1 shows the comparison of the semi-battery performances of examples 1-2, examples 4-9 and comparative examples 1-2, and shows that the expansion rate of the pole pieces of examples 1-2 and examples 4-9 is much lower than that of comparative examples 1 and 2, because the matrix composite material is distributed from the inside to the surface of the microsphere from a large amount to a small amount, the electric conductive agent is distributed differently, so that the porous polymer microsphere has larger internal charge density and small external charge density, the metal lithium is preferentially deposited in the pores inside the microsphere, the volume expansion of the metal lithium deposition is reduced, the volume expansion effect after the lithium metal deposition can be effectively relieved, excessive contact between the metal lithium and the electrolyte is avoided, and the generation of SEI and dead lithium is reduced.
And the first-week coulomb efficiency of examples 1-2 and examples 4-9 is much higher than that of comparative examples 1 and 2, because dendrites of the negative electrode materials in comparative examples 1 and 2 are largely generated, a large amount of dead lithium is formed in the cycle, resulting in loss of active lithium, and lowering the first-week coulomb efficiency of the battery; in the embodiment, lithium metal is deposited in pores inside the polymer, lithium dendrites are not formed to generate dead lithium, and contact with electrolyte is isolated to a certain extent, so that the coulomb efficiency is higher.
Meanwhile, the skeleton composite material has higher porosity and can improve the wettability of electrolyte; the higher specific surface area can provide more reaction sites, so that the charge and discharge efficiency of the battery under high current is enhanced, and the polarization is reduced.
Table 1 comparison of half cell performance of examples and comparative examples
SEM pictures of the pole piece surfaces after depositing the metallic lithium in comparative example 1 and example 1 are shown in fig. 7 and 8, respectively, and from the characterization results, it can be seen that a great amount of lithium dendrites are generated on the pole piece surfaces of the material in comparative example 1, because the conductivity of the outer layer of the microsphere is consistent with that of the inner layer, and the lithium metal does not have a driving force for inward deposition, so that the lithium metal grows on the surfaces of the microsphere to generate dendritic lithium metal; in example 1, since lithium metal was induced to deposit into the microsphere, dendrites were hardly observed on the surface of the electrode sheet, and the effect of suppressing dendrite generation was exhibited.
The performance of the full cells of example 3 and comparative example 4 is shown in fig. 9 and 10, respectively, and it can be seen from fig. 9 and 10 that, after the full cells are assembled, the cell of example 3 can stably cycle for more than 500 cycles at a rate of 0.5C, the capacity retention rate reaches 80%, and the cycle life is far longer than that of the full cell assembled from the material of comparative example 4.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present application, and not for limiting the same; although the application has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the application.
Furthermore, those skilled in the art will appreciate that while some embodiments herein include some features but not others included in other embodiments, combinations of features of different embodiments are meant to be within the scope of the application and form different embodiments. For example, in the claims below, any of the claimed embodiments may be used in any combination. The information disclosed in this background section is only for enhancement of understanding of the general background of the application and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person skilled in the art.
Claims (10)
1. The skeleton composite material is characterized in that the skeleton composite material is porous polymer microspheres, conductive agents are distributed in holes of the porous polymer microspheres, the porous polymer microspheres comprise a high-conductivity inner core and a low-conductivity outer layer coating the high-conductivity inner core, and the conductive agents distributed in the holes of the high-conductivity inner core are higher than the conductive agents distributed in the holes of the low-conductivity outer layer.
2. The matrix composite of claim 1, wherein the porous polymeric microspheres have a mass ratio of conductive agent elements of M1 and the highly conductive core has a mass ratio of conductive agent elements of M2, wherein M1 and M2 satisfy: m1+2% < M2, and M1 and M2 are both in the range of 1% -10%.
3. The matrix composite of claim 1, wherein the porous polymeric microspheres have a conductivity of σ1 and the highly conductive core has a conductivity of σ2, wherein σ1 and σ2 satisfy: sigma 1+0.1S/cm < Sigma 2, and both Sigma 1 and Sigma 2 are greater than 0.1S/cm.
4. The matrix composite of claim 1, wherein the porous polymeric microspheres have a D50 of 2-100 μm.
5. The matrix composite according to any one of claims 1 to 4, wherein the porous polymeric microspheres satisfy at least one of the following conditions:
A. the specific surface area of the porous polymer microsphere is 20-1000 m 2 /g；
B. The true density of the porous polymer microsphere is 1-1.7 g/cm 3 ；
C. The tap density of the porous polymer microsphere is 0.15-0.36 g/cm 3 ；
D. The compaction density of the porous polymer microsphere is 0.7-1.2 g/cm 3 ；
E. The porosity of the porous polymer microsphere is 10% -95%;
F. the porosity of the porous polymer microsphere is 60% -90%.
6. A method of making a skeletal composite material, comprising:
adding a first conductive agent and a first catalyst into a first polymerization raw material solution, and performing a first polymerization reaction to obtain high-conductivity core microspheres;
adding the high-conductivity inner core microsphere into a second polymerization raw material solution, adding a second conductive agent and a second catalyst, and performing a second polymerization reaction on the surface of the high-conductivity inner core microsphere to form a low-conductivity outer layer, so as to obtain a skeleton composite material with a porous polymer microsphere structure;
wherein the mass concentration C1 of the first conductive agent in the first polymerization raw material solution is higher than the mass concentration C2 of the second conductive agent in the second polymerization raw material solution, and C1 > C2+1.
7. The method of preparing a skeletal composite material of claim 6, wherein the method of preparing meets at least one of the following conditions:
a. the first polymerization raw material solution and the second polymerization raw material solution are respectively and independently selected from one or more of resorcinol, phenol, xylenol, urea, formaldehyde, phloroglucinol, cresol, nonylphenol, xylenol, melamine, decaphenol propane, aralkyl phenol, furfuryl alcohol, acrylic acid, phthalic acid, pentanediamine, ethylene, propylene, chloroethylene, acrylonitrile, methacrylic acid, acetaldehyde and vinyl alcohol;
b. the first conductive agent and the second conductive agent are respectively and independently selected from one or a combination of at least two of metal nanowires, metal nanoparticles, conductive carbon black, carbon nanotubes, carbon fibers, graphene nanoparticles and graphene oxide nanoparticles;
c. the mass concentration of the first conductive agent and the second conductive agent is respectively and independently 1-20 g/L;
d. the first catalyst and the second catalyst are respectively and independently selected from any one of formic acid, hydrochloric acid, oxalic acid and benzenesulfonic acid;
e. the first catalyst and the second catalyst respectively regulate the pH value of the reaction solution to be less than 5.
8. The method of preparing a skeletal composite material of claim 6, wherein the method of preparing meets at least one of the following conditions:
(1) The temperature of the first polymerization reaction is 20-90 ℃, and the temperature of the second polymerization reaction is 20-90 ℃;
(2) The time of the first polymerization reaction is 0.5-10 h, and the time of the second polymerization reaction is 1-5 h.
9. A negative electrode sheet, characterized in that a raw material thereof comprises the skeletal composite material of any one of claims 1 to 5.
10. A battery comprising the negative electrode sheet according to claim 9.
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