CN116177538A - Graphene powder material difficult to agglomerate - Google Patents
Graphene powder material difficult to agglomerate Download PDFInfo
- Publication number
- CN116177538A CN116177538A CN202310233501.3A CN202310233501A CN116177538A CN 116177538 A CN116177538 A CN 116177538A CN 202310233501 A CN202310233501 A CN 202310233501A CN 116177538 A CN116177538 A CN 116177538A
- Authority
- CN
- China
- Prior art keywords
- powder material
- graphene
- graphene powder
- intercalation
- easy
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 161
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 100
- 239000000463 material Substances 0.000 title claims abstract description 75
- 239000000843 powder Substances 0.000 title claims abstract description 63
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 13
- 150000001721 carbon Chemical group 0.000 claims abstract description 5
- 238000009830 intercalation Methods 0.000 claims description 39
- 230000002687 intercalation Effects 0.000 claims description 38
- 238000000034 method Methods 0.000 claims description 32
- 239000003054 catalyst Substances 0.000 claims description 19
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 16
- 229910052760 oxygen Inorganic materials 0.000 claims description 15
- 239000001301 oxygen Substances 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 238000010008 shearing Methods 0.000 claims description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 12
- 238000000926 separation method Methods 0.000 claims description 12
- 230000004048 modification Effects 0.000 claims description 10
- 238000012986 modification Methods 0.000 claims description 10
- 230000035484 reaction time Effects 0.000 claims description 9
- 239000000084 colloidal system Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 239000003153 chemical reaction reagent Substances 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 238000003801 milling Methods 0.000 claims description 5
- 238000011049 filling Methods 0.000 claims description 4
- 150000007524 organic acids Chemical class 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 125000004122 cyclic group Chemical group 0.000 claims description 2
- 238000004299 exfoliation Methods 0.000 claims description 2
- 238000005411 Van der Waals force Methods 0.000 abstract description 14
- 230000002776 aggregation Effects 0.000 abstract description 9
- 150000002500 ions Chemical class 0.000 abstract description 6
- 239000000178 monomer Substances 0.000 abstract description 4
- 238000004220 aggregation Methods 0.000 abstract description 3
- 229910002804 graphite Inorganic materials 0.000 description 28
- 239000010439 graphite Substances 0.000 description 28
- 239000002245 particle Substances 0.000 description 14
- 230000008569 process Effects 0.000 description 13
- 239000010410 layer Substances 0.000 description 11
- 239000000243 solution Substances 0.000 description 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 8
- 229910052744 lithium Inorganic materials 0.000 description 8
- 239000002356 single layer Substances 0.000 description 7
- 238000005054 agglomeration Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000003124 biologic agent Substances 0.000 description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 4
- 230000001965 increasing effect Effects 0.000 description 4
- 125000004430 oxygen atom Chemical group O* 0.000 description 4
- 230000009471 action Effects 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 230000032798 delamination Effects 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 229910021382 natural graphite Inorganic materials 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 241000234282 Allium Species 0.000 description 1
- 235000002732 Allium cepa var. cepa Nutrition 0.000 description 1
- 101100280063 Drosophila melanogaster E(spl)malpha-BFM gene Proteins 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- CANRESZKMUPMAE-UHFFFAOYSA-L Zinc lactate Chemical compound [Zn+2].CC(O)C([O-])=O.CC(O)C([O-])=O CANRESZKMUPMAE-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- -1 biological agent Chemical class 0.000 description 1
- 229960004494 calcium gluconate Drugs 0.000 description 1
- 239000004227 calcium gluconate Substances 0.000 description 1
- 235000013927 calcium gluconate Nutrition 0.000 description 1
- MKJXYGKVIBWPFZ-UHFFFAOYSA-L calcium lactate Chemical compound [Ca+2].CC(O)C([O-])=O.CC(O)C([O-])=O MKJXYGKVIBWPFZ-UHFFFAOYSA-L 0.000 description 1
- 229960002401 calcium lactate Drugs 0.000 description 1
- 239000001527 calcium lactate Substances 0.000 description 1
- 235000011086 calcium lactate Nutrition 0.000 description 1
- NEEHYRZPVYRGPP-UHFFFAOYSA-L calcium;2,3,4,5,6-pentahydroxyhexanoate Chemical compound [Ca+2].OCC(O)C(O)C(O)C(O)C([O-])=O.OCC(O)C(O)C(O)C(O)C([O-])=O NEEHYRZPVYRGPP-UHFFFAOYSA-L 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000001066 destructive effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000012377 drug delivery Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 238000005381 potential energy Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 229940050168 zinc lactate Drugs 0.000 description 1
- 235000000193 zinc lactate Nutrition 0.000 description 1
- 239000011576 zinc lactate Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
- C01B32/19—Preparation by exfoliation
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/194—After-treatment
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/02—Single layer graphene
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
- C01B2204/32—Size or surface area
-
- 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)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Nanotechnology (AREA)
- Inorganic Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The embodiment of the invention provides a graphene powder material which is not easy to agglomerate, and comprises two-dimensional graphene with a sheet diameter of 30-150 nm; the thickness of the two-dimensional graphene is the thickness of a single carbon atom layer. The problems that the existing graphene powder material sheet is overlarge in diameter, adhesion is easy to form between graphene and van der Waals force between ions is easy to form aggregation of graphene powder are solved; the two-dimensional graphene has small sheet diameter, and forms carbon element monomers in the aspect of thickness, and due to the small sheet diameter, van der Waals force among powder ions is relatively small, and the small sheet diameter is not easy to adhere, so that the graphene powder material is not easy to agglomerate.
Description
Technical Field
The invention relates to the technical field of graphene materials, in particular to a graphene powder material which is not easy to agglomerate.
Background
Graphene (Graphene) is a new material in which carbon atoms connected by sp2 hybridization are closely packed into a single-layer two-dimensional honeycomb lattice structure. The graphene has excellent optical, electrical and mechanical properties, has important application prospects in the aspects of material science, micro-nano processing, energy sources, biomedicine, drug delivery and the like, and is considered as a revolutionary material in the future.
In order to increase the activity of graphene in application, graphene is usually subjected to oxidation treatment to obtain graphene oxide, and the graphene oxide is used as a single-layer material peeled from the graphene oxide, and can stably exist in an aqueous solution and a polar solvent due to the introduction of a large amount of oxygen-containing groups on the surface and the edge. After oxidation treatment, the graphite oxide still maintains the layered structure of the graphite, and the oxidized graphite has more oxygen-containing functional groups, so that the graphite oxide is more active than graphene in nature, and the graphite oxide can improve the self-property through various reactions with the oxygen-containing functional groups.
However, graphene oxide is large in sheet diameter, on the order of microns; in the oxidation process, graphene is oxidized by strong acid or strong alkali to break carbon-carbon bonds, so that a carbon layer is opened; in the process, a large amount of oxygen groups exist, and a reduction method is needed to remove the oxygen groups in the material by clouding, so that a large amount of holes are formed on the material, the plane area is large, the three-dimensional volume is large, and agglomeration is formed in the solution; in addition, the existing preparation method cannot achieve smaller single-layer sheets, so that the single-layer graphene with larger sheet diameter and the graphene oxide are easy to agglomerate, the agglomerated graphene material cannot be well prepared into a film, even if the formed film is uneven, the performance is not good enough, and therefore, the agglomerated graphene powder material which is difficult to agglomerate is needed.
Disclosure of Invention
The present invention has been made in view of the above problems, and has as its object to provide a graphene powder material which overcomes or at least partially solves the above problems and is not susceptible to agglomeration.
In this application embodiment, a difficult-to-agglomerate graphene powder material is provided, including: two-dimensional graphene with a sheet diameter of 30-150 nm; the thickness of the two-dimensional graphene is the thickness of a single carbon atom layer.
Preferably, the sheet diameter of the two-dimensional graphene is 30-40 nm.
Preferably, the graphene powder material which is not easy to agglomerate is prepared by a precision intercalation mechanical stripping method;
the precision intercalation mechanical stripping method comprises the following steps:
adding the treated modified graphite powder into a first reagent for mixing, and carrying out circulating colloid milling for a plurality of times after mixing until a first foam-shaped mixture is formed; wherein the first reagent consists of a catalyst and deionized water;
transferring the first mixture into an intercalation machine, and injecting hydrogen and oxygen for intercalation shearing to obtain a second mixture; wherein the ratio of the hydrogen to the oxygen is 2:1, the environment of the intercalation machine is 3 atmospheric pressures and 80 ℃, and the reaction time is 1 hour;
and carrying out ultrasonic scattering and separation on the second mixture to obtain a graphene powder material which is not easy to agglomerate, wherein the scattering and separation time is 6 hours.
Preferably, the method further comprises the step of carrying out electromagnetic modification on the graphite powder;
the step of carrying out electromagnetic modification on the graphite powder comprises the following steps:
adding graphite powder into a reaction container, and filling nitrogen into the reaction container until the nitrogen is completely filled into a container cavity of the reaction container;
and starting microwave treatment in the reaction container to obtain modified graphite powder, wherein the treatment temperature is 70-80 ℃ and the reaction time is 1 hour.
Preferably, the mass ratio of the catalyst, the deionized water and the modified graphite powder in the first mixture is 1:20:10.
Preferably, the number of times of the circulating colloid mill is 13.
Preferably, the method further comprises:
transferring the graphene powder material which is not easy to agglomerate into an intercalation machine, and injecting hydrogen and oxygen to carry out intercalation shearing; wherein the ratio of the hydrogen to the oxygen is 2:1, the environment of the intercalation machine is 3 atmospheric pressures and 80 ℃, and the reaction time is 1 hour;
carrying out ultrasonic scattering and separation on the graphene powder material which is not easy to agglomerate and subjected to intercalation shearing, wherein the scattering and separation time is 6 hours;
and repeating the two steps in sequence until the material is completely converted into the graphene powder material which is not easy to agglomerate.
Preferably, the catalyst comprises an organic acid and an organic salt.
The embodiment of the invention has the following advantages:
in the embodiment of the invention, the two-dimensional graphene with the sheet diameter of 30-150 nm solves the problems that the existing graphene powder material has overlarge sheet diameter, adhesion is easy to form between graphene and van der Waals force between ions is easy to form aggregation of graphene powder; the two-dimensional graphene has small sheet diameter, and forms a carbon element monomer in terms of thickness, and the van der Waals force among powder ions is relatively small due to the small sheet diameter, and the small sheet diameter is not easy to adhere, so that the graphene powder material is not easy to agglomerate; after agglomeration, the particle size of the graphene powder material is uneven, and when the graphene powder material is compatible with an organic solution, the graphene powder material cannot well form a solution, and even if the graphene powder material forms a solution, when the graphene powder material is coated on the surface of a carrier, the graphene powder material cannot well form a film due to uneven particle size, and the formed film is uneven or broken.
Drawings
In order to more clearly illustrate the technical solutions of the present invention, the drawings that are needed in the description of the present invention will be briefly described below, it being obvious that the drawings in the following description are only some embodiments of the present invention, and that other drawings may be obtained according to these drawings without inventive effort to a person skilled in the art.
FIG. 1 is a schematic molecular structure diagram of a graphene powder material which is not easy to agglomerate according to an embodiment of the present invention;
fig. 2 is a flowchart of a preparation step of a graphene powder material which is not easy to agglomerate according to an embodiment of the present invention.
Detailed Description
In order that the above-recited objects, features and advantages of the present invention will become more readily apparent, a more particular description of the invention will be rendered by reference to the appended drawings and appended detailed description. It will be apparent that the described embodiments are some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Referring to fig. 1, there is shown a graphene powder material which is not easy to agglomerate and provided by an embodiment of the present invention, including two-dimensional graphene with a sheet diameter of 30 to 150 nm; the thickness of the two-dimensional graphene is the thickness of a single carbon atom layer.
In the embodiment, the two-dimensional graphene with the sheet diameter of 30-150 nm solves the problems that the existing graphene powder material has overlarge sheet diameter (the sheet diameter is about 1 um), adhesion is easy to form between the graphene and van der Waals force between ions is easy to form aggregation of the graphene powder; the two-dimensional graphene has small sheet diameter (the sheet diameter is the radial dimension in the aspect of a plane), and forms a carbon element monomer in the aspect of thickness, and the van der Waals force between powder ions is relatively small due to the small sheet diameter, and the small sheet diameter is not easy to adhere, so that the graphene powder material is not easy to agglomerate; after agglomeration, the particle size of the graphene powder material is uneven, and when the graphene powder material is compatible with an organic solution, the graphene powder material cannot well form a solution, and even if the graphene powder material forms a solution, when the graphene powder material is coated on the surface of a carrier, the graphene powder material cannot well form a film due to uneven particle size, and the formed film is uneven or broken.
It should be noted that, since graphene is composed of carbon monomers, and the thickness of the single-layer carbon atom layer is about 0.334nm, the thickness of the two-dimensional graphene is 0.334nm in the present application; some materials are reported as 0.335nm or other thickness, and should be error due to current measurement accuracy.
In an embodiment of the present application, the sheet diameter of the two-dimensional graphene is preferably 30 to 40nm. The graphene powder material is less prone to agglomeration due to the smaller sheet diameter range.
In an embodiment of the present application, the graphene powder material that is not easy to agglomerate is prepared by a precision intercalation mechanical stripping method; referring to fig. 2, the precision intercalation mechanical exfoliation method includes the steps of:
step S201, adding the processed modified graphite powder into a first reagent for mixing, and performing cyclic colloid milling for a plurality of times after mixing until a first foam-shaped mixture is formed; wherein the first reagent consists of a catalyst and deionized water;
step S202, transferring the first mixture into an intercalation machine, and injecting hydrogen and oxygen for intercalation shearing to obtain a second mixture; wherein the ratio of the hydrogen to the oxygen is 2:1, the environment of the intercalation machine is 3 atmospheric pressures and 80 ℃, and the reaction time is 1 hour;
and step 203, performing ultrasonic scattering and separation on the second mixture to obtain a graphene powder material which is not easy to agglomerate, wherein the scattering and separation time is 6 hours.
In the embodiment, the graphene powder material which is difficult to agglomerate is prepared by the method, so that the problems that graphene with small particle size and thickness cannot be prepared in the prior art, such as the graphene powder material which is difficult to agglomerate, can be well dissolved in an organic solvent to form a solution, and a single-layer graphene film can be formed on a carrier through the solution, and if agglomeration occurs in the film forming process, the film is uneven or partially stacked and the like are solved; when it is used in applications such as electrode materials, the overall thickness of the battery is not uniform because the film is not well formed; according to the graphene powder material which is not easy to agglomerate, the density of the pole piece is increased, and the volume energy density of the battery is improved.
In an embodiment of the present application, the method further includes a step of performing electromagnetic modification on the graphite powder;
the step of carrying out electromagnetic modification on the graphite powder comprises the following steps: adding graphite powder into a reaction container, and filling nitrogen into the reaction container until the nitrogen is completely filled into a container cavity of the reaction container; and starting microwave treatment in the reaction container to obtain modified graphite powder, wherein the treatment temperature is 70-80 ℃ and the reaction time is 1 hour. In the microwave environment of the graphite powder, particles vibrate and rub to peel off the flaky graphite layer which is easy to fall off from the surface layer, and nitrogen is adopted to protect the process and prevent the graphite from burning and exploding.
In the embodiment, the surface of the graphite particles is subjected to physical treatment through a graphite modification process, an orderly arrangement state is formed in an electromagnetic modification link, and a friction effect is formed on the surface of the graphite, so that the surface of the graphite particles is smoother; then, carrying out intercalation treatment on the graphite by an intercalation method of a pure carbon single-layer graphene preparation process, so as to reduce the number of graphite layers; and shearing the graphite surface by a shearing method to form an onion coil structure. By the mode, the form of the natural graphite is changed, and various indexes of the material, such as the conductivity, are improved.
The graphene powder material which is not easy to agglomerate can be used for electrode materials, the volume filling parts of graphene are the same, the larger the particle size is, the wider the distribution is, and the lower the viscosity of slurry is; the small particles can be filled in the gaps of the large particles, which is helpful for increasing the compaction density of the pole pieces and improving the volume energy density of the battery. In addition, the particle morphology also has a great influence on multiplying power, low-temperature performance and the like, and small particles can improve multiplying power performance and prolong cycle life.
In an embodiment of the present application, the mass ratio of the catalyst, the deionized water and the modified graphite powder in the first mixture is 1:20:10. Wherein the catalyst comprises organic acid and organic salt, such as biological agent, such as calcium lactate, calcium gluconate, and zinc lactate.
In an embodiment of the present application, the number of times of the circulating glue grinding is 13, and the better mixing effect is achieved through the glue grinding of 13 times. Specifically, the colloid milling process is that colloid milling equipment rotates at a high speed by a rotor and a matched stator, one of the two is rotated at a high speed, the other is relatively static, the processed modified graphite powder in the first mixture is pressurized by self weight or external pressure (generated by a pump) to generate downward spiral impact force, and the modified graphite powder is subjected to strong shearing force, friction force, high-frequency vibration, high-speed vortex and other physical effects when passing through a gap between a fixed tooth and a rotating tooth (adjustable gap), so that the modified graphite powder is effectively emulsified, dispersed, homogenized and crushed, and the effects of superfine crushing and emulsification of materials are achieved, thereby enabling the graphite powder to be fully contacted with a catalyst in the process, and improving the efficiency of intercalation shearing.
In an embodiment of the present application, further includes: transferring the graphene powder material which is not easy to agglomerate into an intercalation machine, and injecting hydrogen and oxygen to carry out intercalation shearing; wherein the ratio of the hydrogen to the oxygen is 2:1, the environment of the intercalation machine is 3 atmospheric pressures and 80 ℃, and the reaction time is 1 hour; carrying out ultrasonic scattering and separation on the graphene powder material which is not easy to agglomerate and subjected to intercalation shearing, wherein the scattering and separation time is 6 hours; and repeating the two steps in sequence until the material is completely converted into the graphene powder material which is not easy to agglomerate.
In one embodiment, a liquid film intercalation is formed by using the above-described catalyst; specifically, the catalyst is used for inducing energy released in the chemical reaction process between carbon layers, so that the mutual counterbalance of chemical force and Van der Waals force is promoted, the Van der Waals force is destroyed, and the purpose of delamination is achieved. According to the chemical reaction generated by the catalyst, the destructive van der Waals force can be generated without affecting the hexagonal structure of C (carbon) atoms, and according to the characteristic of natural graphite with the C content of 99.9%, the inside of the atomic structure of the catalyst contains a large amount of O (oxygen) atoms besides C atoms under the condition of almost completely containing no heavy metal impurities. The prior art process generally reduces the content thereof by a high-temperature calcination method; in this application, the chemical process can release a certain amount of heat by discharging O atoms through chemical means, and the newly formed oxide is convenient to separate, so we focus on H (hydrogen) atoms and O atoms to combine and react to generate H 2 During the reaction of O.
According to formula H 2 +O 2 ——H 2 O；ΔH＝-285.9kJ·mol -1 Can release 285.9 kJ.mol under ideal condition -1 Energy, but the working environment is in a non-burning state under the protection of protective gas, thusThe test is carried out in the hydrogen atom concentration and pressure change test process, and the alpha particle mass malpha= '4.0026' u, the proton mass mp= '1.00783' u and the electron mass me=5.48 multiplied by 10 ' u are finally obtained -4 u (u is atomic mass unit, 1u=1.6606×10) -27 kg,1u corresponds to an energy of 931.5 MeV), from which the H atom concentration per unit area is determined.
When graphite is subjected to external force, the Van der Waals force is not damaged or the sheet distance is prolonged due to the external force, and the catalyst is required to be used as a bridge to induce interaction between chemical force and Van der Waals force. The catalyst described above in the present application may be any of various inorganic substances, organic substances, biological agents, and the like, and the degree of van der Waals force destruction by using a certain biological agent as a catalyst is optimal. When the biological agent is used as a catalyst, the graphite interlayer spacing is increased from 0.334nm to 0.59-0.65 nm within 5 minutes, and obvious delamination can be observed after about 40 minutes.
The lithium intercalation characteristics of the graphite-based carbon material are: (1) The lithium intercalation potential is low and flat, and can provide high and stable working voltage for the lithium ion battery. Most of lithium intercalation capacity is distributed between 0.00 and 0.20V; (2) High lithium insertion capacity, liC 6 Is 372 mAh.g -1 The method comprises the steps of carrying out a first treatment on the surface of the (3) The lithium intercalation compound has poor compatibility with organic solvents, is easy to generate solvent co-intercalation, and reduces the lithium intercalation performance. Because the graphite spacing (less than or equal to 0.34 nm) is smaller than the crystal plane spacing (less than or equal to 0.37 nm) of the lithium-interlayer compound Li-GIC, the graphite spacing is changed in the charge and discharge process, the graphite layer is easy to peel off and pulverize, and lithium and an organic solvent are intercalated into the graphite layer together to decompose, so that the cycle performance of the battery is influenced.
Advantageously, H is formed by modification of graphite at H atoms, O atoms 2 In the process of O, the heat energy generated by the catalyst is conducted between the carbon layers, so that the van der Waals force between the C atom layers is crushed by the energy, the van der Waals force is pried to achieve the delamination effect, the main purpose is to form a two-dimensional material effect through different intercalation, and the oxygen atom functional group is removed through chemical potential energy, so that the physical property of the material is improved, and when the material is used as a battery material, the charge and discharge performance of graphite can be improved,the specific capacity is improved, so that the prepared battery has good charge and discharge performance and cycle performance.
Advantageously, when used as a negative electrode material, the modified graphite negative electrode material maintains the advantages of a discharge voltage plateau and a higher lithium intercalation capacity of graphite, and improves the compatibility of graphite with an electrolyte and the high-current charge-discharge performance. Because in the graphite with high ordering degree, graphite interlaminar falling caused by graphite expansion during charging is prevented, the specific surface area is increased, C molecules are more ordered, and good electric conduction and electricity storage efficiency is formed.
In this specification, each embodiment is described in a progressive manner, and each embodiment is mainly described by differences from other embodiments, and identical and similar parts between the embodiments are all enough to be referred to each other.
While preferred embodiments of the present invention have been described, additional variations and modifications in those embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. It is therefore intended that the following claims be interpreted as including the preferred embodiment and all such alterations and modifications as fall within the scope of the embodiments of the invention.
Finally, it is further noted that relational terms such as first and second, and the like are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Moreover, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or terminal that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or terminal. Without further limitation, an element defined by the phrase "comprising one … …" does not exclude the presence of other like elements in a process, method, article or terminal device comprising the element.
The graphene powder material which is not easy to agglomerate and provided by the invention is described in detail, and specific examples are applied to illustrate the principle and the implementation mode of the invention, and the description of the examples is only used for helping to understand the method and the core idea of the invention; meanwhile, as those skilled in the art will have variations in the specific embodiments and application scope in accordance with the ideas of the present invention, the present description should not be construed as limiting the present invention in view of the above.
Claims (8)
1. The graphene powder material is characterized by comprising two-dimensional graphene with a sheet diameter of 30-150 nm; the thickness of the two-dimensional graphene is the thickness of a single carbon atom layer.
2. The graphene powder material which is not easy to agglomerate according to claim 1, wherein the sheet diameter of the two-dimensional graphene is 30-40 nm.
3. The non-agglomerated graphene powder material according to claim 1 or 2, wherein the non-agglomerated graphene powder material is prepared by a precision intercalation mechanical exfoliation method;
the precision intercalation mechanical stripping method comprises the following steps:
adding the treated modified graphite powder into a first reagent for mixing, and carrying out circulating colloid milling for a plurality of times after mixing until a first foam-shaped mixture is formed; wherein the first reagent consists of a catalyst and deionized water;
transferring the first mixture into an intercalation machine, and injecting hydrogen and oxygen for intercalation shearing to obtain a second mixture; wherein the ratio of the hydrogen to the oxygen is 2:1, the environment of the intercalation machine is 3 atmospheric pressures and 80 ℃, and the reaction time is 1 hour;
and carrying out ultrasonic scattering and separation on the second mixture to obtain a graphene powder material which is not easy to agglomerate, wherein the scattering and separation time is 6 hours.
4. The non-agglomerated graphene powder material according to claim 3, further comprising the step of electromagnetically modifying the graphite powder;
the step of carrying out electromagnetic modification on the graphite powder comprises the following steps:
adding graphite powder into a reaction container, and filling nitrogen into the reaction container until the nitrogen is completely filled into a container cavity of the reaction container;
and starting microwave treatment in the reaction container to obtain modified graphite powder, wherein the treatment temperature is 70-80 ℃ and the reaction time is 1 hour.
5. The non-agglomerated graphene powder material according to claim 3, wherein the mass ratio of the catalyst, the deionized water, and the modified graphite powder in the first mixture is 1:20:10.
6. The non-agglomerated graphene powder material according to claim 3, wherein the number of cyclic colloid mills is 13.
7. The non-agglomerated graphene powder material according to claim 3, further comprising:
transferring the graphene powder material which is not easy to agglomerate into an intercalation machine, and injecting hydrogen and oxygen to carry out intercalation shearing; wherein the ratio of the hydrogen to the oxygen is 2:1, the environment of the intercalation machine is 3 atmospheric pressures and 80 ℃, and the reaction time is 1 hour;
carrying out ultrasonic scattering and separation on the graphene powder material which is not easy to agglomerate and subjected to intercalation shearing, wherein the scattering and separation time is 6 hours;
and repeating the two steps in sequence until the material is completely converted into the graphene powder material which is not easy to agglomerate.
8. The non-agglomerated graphene powder material of claim 3, wherein the catalyst comprises an organic acid and an organic salt.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310233501.3A CN116177538A (en) | 2023-03-02 | 2023-03-02 | Graphene powder material difficult to agglomerate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310233501.3A CN116177538A (en) | 2023-03-02 | 2023-03-02 | Graphene powder material difficult to agglomerate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116177538A true CN116177538A (en) | 2023-05-30 |
Family
ID=86448753
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310233501.3A Pending CN116177538A (en) | 2023-03-02 | 2023-03-02 | Graphene powder material difficult to agglomerate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116177538A (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20160244333A1 (en) * | 2015-02-24 | 2016-08-25 | Aruna Zhamu | Environmentally benign production of graphene materials |
| CN107215867A (en) * | 2016-03-22 | 2017-09-29 | 中国科学院金属研究所 | A kind of method that serialization prepares graphene oxide microplate |
| CN115959655A (en) * | 2022-12-12 | 2023-04-14 | 上海巴库斯超导新材料有限公司 | Graphene film preparation method and graphene film |
| CN116835577A (en) * | 2022-12-12 | 2023-10-03 | 深圳市中明华顶胜新材料有限公司 | Preparation method of pure carbon single-layer graphene material and single-layer graphene |
-
2023
- 2023-03-02 CN CN202310233501.3A patent/CN116177538A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20160244333A1 (en) * | 2015-02-24 | 2016-08-25 | Aruna Zhamu | Environmentally benign production of graphene materials |
| CN107215867A (en) * | 2016-03-22 | 2017-09-29 | 中国科学院金属研究所 | A kind of method that serialization prepares graphene oxide microplate |
| CN115959655A (en) * | 2022-12-12 | 2023-04-14 | 上海巴库斯超导新材料有限公司 | Graphene film preparation method and graphene film |
| CN116835577A (en) * | 2022-12-12 | 2023-10-03 | 深圳市中明华顶胜新材料有限公司 | Preparation method of pure carbon single-layer graphene material and single-layer graphene |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zhang et al. | Carbon dots@ rGO paper as freestanding and flexible potassium‐ion batteries anode | |
| Azam et al. | Recent advances of silicon, carbon composites and tin oxide as new anode materials for lithium-ion battery: A comprehensive review | |
| Chen et al. | Nanoscale engineering of heterostructured anode materials for boosting lithium‐ion storage | |
| Chen et al. | In situ generation of few‐layer graphene coatings on SnO2‐SiC core‐shell nanoparticles for high‐performance lithium‐ion storage | |
| Yang et al. | Bismuth Nanoparticles Embedded in Carbon Spheres as Anode Materials for Sodium/Lithium‐Ion Batteries | |
| Ng et al. | Amorphous carbon-coated silicon nanocomposites: a low-temperature synthesis via spray pyrolysis and their application as high-capacity anodes for lithium-ion batteries | |
| CN103474631B (en) | Silicon monoxide composite negative electrode material for lithium ion battery, preparation method and lithium ion battery | |
| Li et al. | A black phosphorus/Ti 3 C 2 MXene nanocomposite for sodium-ion batteries: a combined experimental and theoretical study | |
| Chen et al. | Rapid, in situ synthesis of high capacity battery anodes through high temperature radiation-based thermal shock | |
| Qiu et al. | Antimony nanocrystals encapsulated in carbon microspheres synthesized by a facile self-catalyzing solvothermal method for high-performance sodium-ion battery anodes | |
| Xiao et al. | High-capacity and self-stabilized manganese carbonate microspheres as anode material for lithium-ion batteries | |
| Jiang et al. | High capacitive antimonene/CNT/PANI free‐standing electrodes for flexible supercapacitor engaged with self‐healing function | |
| CN105932256B (en) | Graphene-based FeS2Nano material and preparation and application thereof | |
| Wu et al. | High-performance SiO/C as anode materials for lithium-ion batteries using commercial SiO and glucose as raw materials | |
| Shuvo et al. | Investigation of modified graphene for energy storage applications | |
| Talluri et al. | Nanocomposites of digestively ripened copper oxide quantum dots and graphene oxide as a binder free battery-like supercapacitor electrode material | |
| JP6082395B2 (en) | Structurally stable active materials for battery electrodes | |
| Zhang et al. | Silicon-multi-walled carbon nanotubes-carbon microspherical composite as high-performance anode for lithium-ion batteries | |
| CN116835577A (en) | Preparation method of pure carbon single-layer graphene material and single-layer graphene | |
| CN105655589A (en) | Graphene composite material and preparation method thereof | |
| Chen et al. | CNTs–C@ TiO2 composites with 3D networks as anode material for lithium/sodium ion batteries | |
| CN110112405B (en) | Core-shell structure silicon/carbon fiber flexible composite electrode material and preparation method and application thereof | |
| Wei et al. | Designed formation of yolk–shell-like N-doped carbon-coated Si nanoparticles by a facile method for lithium-ion battery anodes | |
| Stenina et al. | Effect of carbon and N-doped carbon nanomaterials on the electrochemical performance of lithium titanate-based composites | |
| Yan et al. | Millimeter silicon-derived secondary submicron materials as high-initial coulombic efficiency anode for lithium-ion batteries |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |