CN115838163A - Porous carbon material and preparation method thereof, negative electrode plate and lithium ion battery - Google Patents
Porous carbon material and preparation method thereof, negative electrode plate and lithium ion battery Download PDFInfo
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Battery Electrode And Active Subsutance (AREA)
Abstract
The utility model relates to a porous carbon material, its inside has the hole, through the lithium affinity nature material that has lower nucleation overpotential of downthehole introduction at porous carbon material, make can induce lithium and separate out at downthehole with the form that lithium affinity nature material formed the alloy in charging process, therefore make the inside hole of porous carbon material become and store up the lithium space, make originally can separate out at the lithium metal that the pole piece surface was separated out in the low CB value system downthehole with the lithium alloy form, thereby the lithium space of storing up of porous carbon material has been improved. In addition, through forming the coating on the surface of the porous carbon material, the electrolyte can be prevented from entering the porous carbon material, and the loss caused by contact reaction between the electrolyte and the precipitated lithium alloy is avoided. Meanwhile, by reasonably designing the ratio of the mass of the lithium-philic substances to the volume of the holes, the holes containing the lithium-philic substances can be completely filled with the lithium alloy which is induced to be precipitated as much as possible, and the capacity of the holes is fully utilized.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a porous carbon material and a preparation method thereof, a negative electrode plate, a lithium ion battery, a battery module, a battery pack and an electric device.
Background
The lithium ion battery cathode material mainly comprises artificial graphite, hard carbon material and the like. Artificial graphite is the most mature negative electrode material applied in the current lithium ion battery, but the energy density is close to the theoretical limit. With the iterative upgrade of new energy technology, the urgent need of mileage anxiety is being solved, and the design demand of high energy density battery cells (400 Wh/kg) is increasing. Compared with graphite, the hard carbon material has a larger intercalation structure and more defects, so that the hard carbon material has higher gram capacity and becomes a new research hotspot of the cathode material. However, the hard carbon material has insufficient lithium storage space. Researchers are urgently required to develop hard carbon materials having high lithium storage space.
Disclosure of Invention
In view of the problems in the background art, the present application provides a porous carbon material having a high lithium storage space.
The porous carbon material provided by the first aspect of the present application has pores therein. The pores contain a lithium-philic material. The ratio of the mass of the lithium-philic substance to the volume of the holes is 3:1-32. The surface of the porous carbon material is provided with a coating layer.
In the technical scheme of this application embodiment, through the lithium affinity nature substance that has lower nucleation overpotential of downthehole introduction at porous carbon material for can induce lithium and form the form of alloy with lithium affinity nature substance and separate out in downthehole in charging process, therefore make the inside hole of porous carbon material become and store up lithium space, make among the low CB value system originally can separate out lithium metal that can separate out on the pole piece surface can separate out with the lithium alloy form in downthehole, thereby improved porous carbon material's lithium storage space. However, in the prior art, the pores of the porous carbon material do not contain lithium-philic substances, so that the porous carbon material cannot become a lithium storage space. In addition, through forming the coating on the surface of the porous carbon material, the electrolyte can be prevented from entering the porous carbon material, and the loss caused by contact reaction between the electrolyte and the precipitated lithium alloy is avoided. Meanwhile, by reasonably designing the ratio of the mass of the lithium-philic substances to the volume of the holes, the holes containing the lithium-philic substances can be completely filled with the lithium alloy which is induced to be precipitated as much as possible, and the capacity of the holes is fully utilized.
In addition, since the lithium-philic substance is filled in the pores of the porous carbon material, the porous carbon material also has a high compacted density. Therefore, the use of the porous carbon material of the present application also enables an increase in the volumetric energy density of the battery.
In some embodiments, according to the first aspect, which proposes the first example of the first aspect, the ratio of the mass of the lithium-philic substance to the volume of the pores is 10.
In the design, the ratio of the mass of the lithium-philic substances to the volume of the holes is further optimized, so that the holes containing the lithium-philic substances can be completely filled with the lithium alloy subjected to induced precipitation as much as possible, and the lithium storage space of the porous carbon material is increased. If Kong Naqin the lithium material is too high, a small amount of lithium metal is combined with the lithium-philic material in an alloying manner, and most of lithium is still precipitated on the surface of the pole piece in the form of lithium metal; if the Kong Naqin content of lithium is too low, lithium metal cannot be precipitated in the pores of the porous carbon material, i.e., the space in the pores becomes a dead space, and lithium still precipitates on the surface of the pole piece in the form of lithium metal.
In some embodiments, according to the first aspect, which proposes the second example of the first aspect, the lithium-philic substance is one or more of metals Zn, ag, au, ga, in, sn and oxides thereof.
In the design, the lithium-philic substances have lower nucleation overpotential, so that lithium metal can be induced to be separated out in the hole in a lithium alloy form in the charging process, and the lithium metal simple substance is prevented from being separated out on the surface of a pole piece or on the surface of a coating layer of a porous carbon material, so that the lithium metal simple substance is prevented from being contacted with electrolyte and being subjected to irreversible reaction to be consumed, the capacity is reduced, and even the battery core is prevented from losing efficacy.
In some embodiments, according to the first aspect which is the third example of the first aspect, the clad layer has a thickness of 50 to 350nm.
In the design, through optimizing the thickness of the coating layer, the electrolyte can be more effectively prevented from entering the porous carbon material, and the contact reaction of the electrolyte and the precipitated lithium alloy is avoided.
In some embodiments, according to the first aspect, which proposes the fourth example of the first aspect, the pores have a pore diameter of 0.1 to 10 μm.
In the design, the small aperture can lead to insufficient lithium storage space, the requirement of high energy density of the battery cell 400Wh/kg is difficult to meet, and the large aperture can cause difficulty increase of the phase transmission process of lithium precipitation and lithium removal in the hole.
In some embodiments, according to the first aspect, a fifth example of the first aspect is provided, wherein a mass ratio of the lithium-philic substance to the porous carbon material is 9:1 to 1.5.
Since the amount of the lithium-philic substance determines the amount of lithium deposition, the content of the lithium-philic substance, that is, the mass ratio of the lithium-philic substance to the porous carbon material can be increased appropriately in order to increase the amount of lithium deposition and further increase the lithium storage space of the porous carbon material.
In some embodiments, according to the first aspect, it is provided that the porous carbon material is in a granular form. The particle size of the particulate porous carbon material is 5 to 30 μm, for example, 5 μm, 10 μm, 15 μm, 20 μm, 25 μm, or 30 μm.
In this design, by optimizing the particle diameter of the particles, it is more favorable to form pores containing the lithium-philic substance inside the particles.
A second aspect of the present application provides a method for producing a porous carbon material, comprising:
mixing resin, lithium-philic chloride salt, a pore-forming agent and a solvent to obtain a mixture;
curing the mixture to obtain a carbon precursor;
carrying out pyrolysis carbonization treatment on the carbon precursor, and after acid washing, obtaining a porous carbon material; and
the obtained porous carbon material is surface-coated to form a coating layer.
According to the technical scheme, the hole structure containing the lithium-philic substance can be formed in the carbon material by regulating and controlling the technological parameters, and the reasonable proportional relation between the mass of the lithium-philic substance and the volume of the hole is obtained.
In some embodiments, according to the second aspect, which proposes the first example of the second aspect, the ratio of the mass of the resin to the total mass of the lithium-philic chloride salt and the pore former is 1:1-1.
In the design, the ratio of the mass of the lithium-philic substance to the volume of the hole is favorably controlled within a reasonable range by optimizing the consumption of the raw materials, so that the induced and precipitated lithium alloy completely fills the hole containing the lithium-philic substance as far as possible, and the lithium storage space of the porous carbon material is improved.
In some embodiments, according to the second aspect, which is set forth as a second example of the second aspect, the temperature of the pyrolysis carbonization treatment is 600 ℃ to 1200 ℃ for 0.5 to 6 hours.
In the design, the temperature and the time of the pyrolysis carbonization treatment are optimized, so that the size of pores in the formed porous carbon material can be controlled more favorably.
In some embodiments, according to the second aspect, which is a third example of the second aspect, the pickling temperature is 30 to 60 ℃ and the pickling time is 30 to 60min.
During acid washing, the control of acid washing time and temperature is very important, and the loss of lithium-philic substances in the porous carbon material is easily caused by overlong acid washing time and overhigh acid washing temperature. In addition, the selection of the acid washing process parameters is also closely related to the addition amount of the lithium-philic chloride salt and the pore-forming agent.
In some embodiments, according to the second aspect, which proposes a fourth example of the second aspect, the curing process comprises: and (3) carrying out liquid curing treatment on the mixture, crushing the obtained massive solid, carrying out reinforced curing treatment, and crushing again to obtain the carbon precursor.
In the design, the dehydration and solidification effects can be further enhanced through crushing and strengthening solidification treatment, so that the composite resin structure is more stable.
In some embodiments, according to the second aspect, there is provided a fifth example of the second aspect, wherein the temperature of the liquid curing process is 60 to 150 ℃. The temperature of the strengthening and curing treatment is 100-200 ℃.
In this design, the stability of the composite resin structure can be improved by optimizing the temperature of the liquid curing process and the strengthening curing process.
In some embodiments, according to the second aspect, a sixth example of the second aspect is provided, in which the obtained porous carbon material is surface-coated with graphite or resin, and after sintering, a coating layer is formed.
In the design, through optimizing the coating material, the electrolyte can be more effectively prevented from entering the porous carbon material, and the contact reaction between the electrolyte and the precipitated lithium alloy is avoided.
In some embodiments, according to the second aspect, which proposes a seventh example of the second aspect, the lithium-philic chloride salt is one or more of zinc chloride, silver chloride, gold chloride, gallium chloride, indium chloride, and tin chloride.
After the pyrolysis carbonization treatment, the lithium-philic chloride salt is converted into corresponding metal simple substances and metal oxides. The metal simple substances and the metal oxides are lithium-philic substances, have lower nucleation overpotential, and can induce lithium metal to be precipitated in pores in the form of lithium alloy in the charging process.
A third aspect of the present application provides a negative electrode sheet comprising the porous carbon material according to the first aspect of the present application or the porous carbon material obtained by the preparation method according to the second aspect of the present application.
In the technical solution of the embodiment of the present application, due to the adoption of the porous carbon material of the first aspect of the present application or the porous carbon material obtained by the preparation method of the second aspect of the present application, the negative electrode sheet of the present application has a high lithium storage space, a high compacted density and a high volumetric energy density.
A fourth aspect of the present application provides a lithium ion battery comprising the negative electrode tab of the third aspect of the present application.
In the technical solution of the embodiment of the present application, due to the adoption of the porous carbon material of the first aspect of the present application or the porous carbon material obtained by the preparation method of the second aspect of the present application, the lithium ion battery of the present application has a high lithium storage space, a high compacted density and a high volumetric energy density.
A fifth aspect of the present application provides a battery module including the lithium ion battery of the fourth aspect of the present application.
In the technical solution of the embodiment of the present application, due to the use of the porous carbon material of the first aspect of the present application or the porous carbon material obtained by the preparation method of the second aspect of the present application, the battery module of the present application has a high lithium storage space, a high compacted density, and a high volumetric energy density.
A sixth aspect of the present application provides a battery pack including the battery module according to the sixth aspect of the present application.
In the technical solution of the embodiment of the present application, due to the use of the porous carbon material of the first aspect of the present application or the porous carbon material obtained by the preparation method according to the second aspect of the present application, the battery pack of the present application has a high lithium storage space, a high compacted density, and a high volumetric energy density.
A seventh aspect of the present application provides an electric device including at least one of the lithium ion battery according to the fourth aspect of the present application, the battery module according to the fifth aspect of the present application, and the battery pack according to the sixth aspect of the present application.
In the technical solution of the embodiment of the present application, due to the use of the porous carbon material of the first aspect of the present application or the porous carbon material obtained by the preparation method of the second aspect of the present application, the electric device of the present application has a high lithium storage space, a high compaction density, and a high volumetric energy density.
The foregoing description is only an overview of the technical solutions of the present application, and the following detailed description of the present application is given to enable the technical means of the present application to be more clearly understood and to enable the above and other objects, features, and advantages of the present application to be more clearly understood.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments of the present invention will be briefly described below, and it is obvious that the drawings described below are only some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to the drawings without creative efforts.
Fig. 1 is a Scanning Electron Microscope (SEM) image of the surface morphology of the porous carbon material prepared in example 1 of the present application.
Fig. 2 is a scanning electron microscope image of the cross-sectional morphology of the porous carbon material prepared in example 1 of the present application.
Fig. 3 is a scanning electron microscope image of the cross-sectional morphology of the porous carbon material prepared in example 1 of the present application after lithium deposition.
Fig. 4 is a scanning electron microscope image of the cross-sectional morphology of the porous carbon material prepared in example 1 of the present application after delithiation.
Fig. 5 is a cross-sectional element distribution diagram of the porous carbon material prepared in example 1 of the present application after lithium deposition.
Fig. 6 is a cross-sectional element distribution diagram of the porous carbon material prepared in example 1 of the present application after delithiation.
Detailed Description
In order to make the purpose, technical solution and advantageous technical effects of the present invention clearer, the present invention is described in detail with reference to specific embodiments below. It should be understood that the embodiments described in this specification are only for the purpose of explaining the present application and are not intended to limit the present application.
For the sake of brevity, only some numerical ranges are explicitly disclosed herein. However, any lower limit may be combined with any upper limit to form ranges not explicitly recited; and any lower limit may be combined with any other lower limit to form a range not explicitly recited, and similarly any upper limit may be combined with any other upper limit to form a range not explicitly recited. Also, although not explicitly recited, each point or individual numerical value between the endpoints of a range is encompassed within that range. Thus, each point or individual value can form a range not explicitly recited as its own lower or upper limit in combination with any other point or individual value or in combination with other lower or upper limits.
In the description herein, it is to be noted that, unless otherwise specified, "above" and "below" are inclusive, and "one or more" of "a plurality" means two or more (including two).
The above summary of the present application is not intended to describe each disclosed embodiment or every implementation of the present application. The following description more particularly exemplifies illustrative embodiments. At various points throughout this application, guidance is provided through a list of embodiments that can be used in various combinations. In each instance, the list is provided only as a representative group and should not be construed as exhaustive.
The lithium ion battery cathode material mainly comprises artificial graphite, hard carbon material and the like. Artificial graphite is the most mature anode material applied in the current lithium ion battery, but the energy density is close to the theoretical limit. With the iterative upgrade of new energy technologies, the urgency of resolving mileage anxiety is increasing, and the demand for high energy density cells (e.g., 400 Wh/kg) is increasing. Compared with graphite, the hard carbon material has a larger intercalation structure and more defects, so that the hard carbon material has higher gram capacity and becomes a new research hotspot of the cathode material. However, the hard carbon material has insufficient lithium storage space. Researchers are urgently required to develop hard carbon materials having high lithium storage space.
For hard carbon materials, a gram capacity of up to about 800mAh/g is required to achieve an energy density requirement of 400 Wh/kg. However, the gram capacities of today's preferred hard carbon materials are on the order of 400-500mAh/g, making it difficult to achieve the design requirements of 400Wh/kg high energy density. Therefore, a low CB value (ratio of negative electrode surface capacity to positive electrode surface capacity) (CB value may be 0.6, for example) system design becomes an indispensable choice at present. In a low CB value system, a part of lithium is intercalated into the carbon material in a lithiated form, and the other part of lithium is precipitated on the surface of the pole piece in a lithium metal form because no more lithium storage space exists in the carbon material, so that the cycle life is ensured. However, lithium precipitated on the surface of the pole piece in the form of lithium metal has serious dendrite growth during the circulation process, and is rapidly lost in direct contact with the electrolyte, causing rapid decay of the cycle life.
For the system with low CB value, in order to reduce the occurrence of lithium precipitation on the surface of the pole piece, the inventor carries out intensive research and proposes a solution, namely, the lithium storage space in the carbon material is increased. Specifically, the inventor designs a porous carbon material, the porous carbon material has a pore structure inside, and lithium-philic substances with lower nucleation overpotential are introduced into pores of the porous carbon material, so that lithium can be induced to be precipitated in the pores in an alloy form with the lithium-philic substances in the charging process, and the pores in the porous carbon material become lithium storage spaces, and lithium metal which is originally precipitated on the surface of a pole piece in a low CB value system can be precipitated in the pores, so that the lithium storage spaces of the carbon material are improved, and if the lithium metal is precipitated in the pores, a battery cell basically does not expand. However, in the prior art, the pores of the porous carbon material do not contain lithium-philic substances, so that the porous carbon material cannot become a lithium storage space.
In addition, through forming the coating on the surface of the porous carbon material, the electrolyte can be prevented from entering the porous carbon material, and the loss caused by contact reaction between the electrolyte and the precipitated lithium alloy is avoided. Meanwhile, by reasonably designing the ratio of the mass of the lithium-philic substances to the volume of the holes, the holes containing the lithium-philic substances can be completely filled with the lithium alloy which is induced to be precipitated as much as possible, and the capacity of the holes is fully utilized.
For a 400Wh/kg energy density design, a CB value of 0.6 may be used herein. Of course, the magnitude of the CB value can be designed according to the specific energy density, and generally, the higher the energy density, the smaller the CB value can be.
The technical scheme described in the embodiment of the application is suitable for a porous carbon material, and is also suitable for a preparation process of the porous carbon material, a lithium ion battery using a negative electrode plate made of a porous carbon material, a battery module using the lithium ion battery, a battery pack using the battery module, and an electric device using at least one of the lithium ion battery, the battery module and the battery pack.
In a first aspect, according to some embodiments of the present application, there is provided a porous carbon material having pores therein. The pores contain a lithium-philic substance. The mass of the lithium-philic substance to volume of the pores is 3:1-32. The surface of the porous carbon material is provided with a coating layer.
In the technical scheme of this application embodiment, through the lithium affinity nature substance that has lower nucleation overpotential of downthehole introduction at porous carbon material for can induce lithium and form the form of alloy with lithium affinity nature substance and separate out in downthehole in charging process, therefore make the inside hole of porous carbon material become and store up lithium space, make among the low CB value system originally can separate out lithium metal that can separate out on the pole piece surface can separate out with the lithium alloy form in downthehole, thereby improved porous carbon material's lithium storage space. However, in the prior art, the pores of the porous carbon material do not contain lithium-philic substances, so that the porous carbon material cannot become a lithium storage space. In addition, through forming the coating on the surface of the porous carbon material, the electrolyte can be prevented from entering the porous carbon material, and the loss caused by contact reaction between the electrolyte and the precipitated lithium alloy is avoided. Meanwhile, by reasonably designing the ratio of the mass of the lithium-philic substances to the volume of the holes, the holes containing the lithium-philic substances can be completely filled with the lithium alloy which is induced to be precipitated as much as possible, and the capacity of the holes is fully utilized. In addition, since the lithium-philic substance is filled in the pores of the porous carbon material, the porous carbon material also has a high compacted density. Therefore, the use of the porous carbon material of the present application also enables an increase in the volumetric energy density of the battery.
In some embodiments, the porous carbon material is preferably a porous hard carbon material. The hard carbon material has a large interlayer distance, which facilitates the intercalation and deintercalation of lithium ions, and thus has excellent charge and discharge properties.
In some embodiments, the pores containing the lithium-philic substance in the porous carbon material are typically of a micron-scale pore structure. The micro-scale pore structure is in a closed pore form observed from a micro scale (i.e. from a macro scale), and in the prior art, the closed pores cannot transport lithium ions, so that electrochemical reaction cannot be carried out in the closed pores, and belong to ineffective pores. According to the invention, the lithium-philic substance with lower nucleation overpotential is introduced into the closed pores, and the power transmission parameters of the closed pores are changed, so that the closed pores are used as lithium storage spaces and become effective electrochemical reaction sites. From the analysis on the nanometer scale (i.e. from the microcosmic scale), in principle, a nanometer-scale pore canal communicated with the micron-scale pore structure exists around the micron-scale pore structure, one end of the nanometer-scale pore canal is communicated with the micron-scale pore structure, and the other end of the nanometer-scale pore canal extends to the surface of the porous carbon material. The nanoscale pore channels are formed by gas overflow in the pyrolysis carbonization treatment process, and lithium-philic substances are not included in the nanoscale pore channels. In order to thoroughly solve the risk that the electrolyte permeates into the micron-scale pore structure through the nanometer-scale pore channel, the inventor forms a coating layer on the surface of the porous carbon material.
In some embodiments of the present application, the microscale pore structure may be an irregular or regular sphere, such as an ellipsoid.
In some embodiments, according to the first aspect, which proposes the first example of the first aspect, the ratio of the mass of the lithium-philic substance to the volume of the pores may be 10.
In the design, the ratio of the mass of the lithium-philic substance to the volume of the pores is further optimized, so that the pores containing the lithium-philic substance can be completely filled with the lithium alloy which is induced to be precipitated as far as possible, and the lithium storage space of the porous carbon material is improved.
In some embodiments of the present application, the mass of the lithium-philic species to volume of the pores may be 10.
In some embodiments, according to the first aspect, which proposes the second example of the first aspect, the lithium-philic substance is one or more of metals Zn, ag, au, ga, in, sn and oxides thereof.
In the design, the lithium-philic substances have lower nucleation overpotential, so that lithium metal can be induced to be separated out in the hole in a lithium alloy form in the charging process, and the lithium metal simple substance is prevented from being separated out on the surface of a pole piece or on the surface of a coating layer of a porous carbon material, so that the lithium metal simple substance is prevented from being contacted with electrolyte and being subjected to irreversible reaction to be consumed, the capacity is reduced, and even the battery core is prevented from losing efficacy.
In some embodiments of the present application, the lithium-philic substance may be one or more of the metals Zn, ag, sn, and oxides thereof. In some embodiments, the lithium-philic substance may be one or more of a mixture of a metal Zn and an oxide thereof, a mixture of a metal Ag and an oxide thereof, and a mixture of a metal Sn and an oxide thereof. Preferably, the lithium-philic substance may be a mixture of metallic Zn and its oxides.
In some embodiments, according to the first aspect, which proposes the third example of the first aspect, the clad layer may have a thickness of 50 to 350nm.
In the design, through optimizing the thickness of the coating layer, the electrolyte can be more effectively prevented from entering the porous carbon material, and the contact reaction of the electrolyte and the precipitated lithium alloy is avoided. In addition, a coating layer is formed on the surface of the porous carbon material, so that holes on the surface of the porous carbon material can be filled, the specific surface area of the porous carbon material is reduced, a better SEI (solid electrolyte interphase) film layer is favorably formed, and the first effect and the cycle life of the battery are improved.
In some embodiments of the present application, the coating may have a thickness of 80-310nm, for example, 80nm, 90nm, 100nm, 110nm, 120nm, 130nm, 140nm, 150nm, 160nm, 170nm, 180nm, 190nm, 200nm, 210nm, 220nm, 230nm, 240nm, 250nm, 260nm, 270nm, 280nm, 290nm, 300nm, or 310nm.
In some embodiments of the present application, the material of the coating layer may be graphite or resin, such as epoxy resin, phenolic resin, and polyamide resin.
In some embodiments according to the first aspect which proposes the fourth example of the first aspect, the pores have a pore diameter of 0.1 to 10 μm.
In the design, the small aperture can lead to insufficient lithium storage space, the requirement of high energy density of the battery cell 400Wh/kg is difficult to meet, and the large aperture can cause difficulty increase of the phase transmission process of lithium precipitation and lithium removal in the hole.
In some embodiments of the present application, the pores may have a pore size of 0.1 μm, 0.5 μm, 1 μm, 2 μm, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm. In principle, many pores of different pore diameters exist inside the porous carbon material. Thus, the pore size of the pores is in a certain range, for example, may be in the range of 0.1 to 10 μm or 1 to 5 μm.
In some embodiments, according to the first aspect which proposes the fifth example of the first aspect, the mass ratio of the lithium-philic substance to the porous carbon material is 9:1 to 1.5.
Since the amount of the lithium-philic substance determines the amount of lithium deposition, the content of the lithium-philic substance, that is, the mass ratio of the lithium-philic substance to the porous carbon material can be increased as appropriate in order to increase the amount of lithium deposition and further increase the lithium storage space of the porous carbon material.
In some embodiments of the present application, the mass ratio of the lithium philic substance to the porous carbon material may be 8:1-2:1, for example 8:1, 7:1, 6:1, 5:1, 4:1, 3:1, or 2:1.
In some embodiments, according to the first aspect, it is provided that the porous carbon material is in a granular form. The particle diameter of the particulate porous carbon material is 10 to 30 μm.
In this design, by optimizing the particle diameter of the particles, it is more favorable to form pores containing the lithium-philic substance inside the particles.
The principle of lithium deposition on the porous carbon material negative electrode will be analyzed below.
The lithium precipitation on the porous carbon material negative electrode comprises: and (3) precipitating lithium in the pores and precipitating lithium on the surface of the pole piece or the surface of the carbon material. In the present application, the principle of lithium deposition in the pores is: firstly, lithium ions obtain an electron to form a metallic lithium simple substance, and then the lithium simple substance reacts with a carbon simple substance in a porous carbon material to generate LiC 6 Finally, the lithium-philic substance is reacted with LiC 6 Reacting to produce the lithium alloy. The principle of lithium precipitation on the surface of the pole piece or the surface of the carbon material is as follows: the lithium ions obtain an electron to form a metallic lithium simple substance. Because the lithium-philic substance has lower nucleation overpotential, lithium metal can be induced to be separated out in the hole in a lithium alloy form in the charging process, and the separation of the lithium metal simple substance on the surface of a pole piece or the surface of a carbon material is avoided, so that the situation that the lithium metal simple substance is contacted with electrolyte and generates irreversible reaction to be consumed, the capacity is reduced, and even the battery core is invalid is avoided.
A second aspect of the present application provides a method for producing a porous carbon material, comprising:
mixing resin, lithium-philic chloride salt, a pore-forming agent and a solvent to obtain a mixture;
curing the mixture to obtain a carbon precursor;
carrying out pyrolysis carbonization treatment on the carbon precursor, and after acid washing, obtaining a porous carbon material; and
and coating the surface of the obtained porous carbon material to form a coating layer.
According to the technical scheme, the hole structure containing the lithium-philic substance can be formed in the carbon material by regulating and controlling the technological parameters, and the reasonable proportional relation between the mass of the lithium-philic substance and the volume of the hole is obtained.
In some embodiments of the present application, the resin may be one or more of a phenolic resin, an epoxy resin, and a polyurethane. The phenolic resin may be one or both of a novolac phenolic resin and a resole phenolic resin. Of course, the resins of the present application may also be other resins commonly used in the art for pyrolysis to produce hard carbon materials. In some embodiments, the solids content of the resin may be 70% to 80%.
In some embodiments of the present application, the pore former may be one or both of sodium chloride and potassium chloride. The pore-forming agent can adjust the pore diameter of pores, but does not generate lithium-philic substances after pyrolysis carbonization treatment.
In some embodiments herein, the solvent may be one or more of methanol, ethanol, ethylene glycol, polyethylene glycol, glycerol, isopropanol, and other polyols. The specific kind of the solvent is not particularly limited as long as the resin can be dissolved.
In some embodiments of the present application, the mass ratio of resin to solvent can be 1:1-100, for example can be 1:1, 1, 10, 1.
In some embodiments of the present application, the mixture may be obtained by stirring, which may be at a speed of 100 to 1500r/min.
In some embodiments, according to the second aspect, which proposes the first example of the second aspect, the ratio of the mass of the resin to the total mass of the lithium-philic chloride salt and the pore former is 1:1-1.
In the design, the ratio of the mass of the lithium-philic substance to the volume of the hole is favorably controlled within a reasonable range by optimizing the consumption of the raw materials, so that the induced and precipitated lithium alloy completely fills the hole containing the lithium-philic substance as far as possible, and the lithium storage space of the porous carbon material is improved.
In some embodiments of the present application, the ratio of the mass of resin to the total mass of lithium-philic chloride salt and pore former may be, for example, 1:1, 1, 20, 1, 30, 1, 40, 50, 1, 60, 1, 70, 1. Alternatively, the ratio of the mass of resin to the total mass of lithium-philic chloride salt and pore former may be 1.
In some embodiments, according to the second aspect, a second example of the second aspect is provided, wherein the temperature of the pyrolysis carbonization treatment is 600 ℃ to 1200 ℃ and the time is 0.5 to 6 hours.
In the design, the temperature and the time of the pyrolysis carbonization treatment are optimized, so that the size of the pores in the formed porous carbon material can be controlled more favorably.
In some embodiments of the present application, the temperature of the pyrolytic carbonization process may be 600 ℃ to 1200 ℃, for example may be 600 ℃, 700 ℃, 800 ℃, 900 ℃, 1000 ℃, 1100 ℃ or 1200 ℃, preferably 800 ℃ to 1000 ℃. The pyrolysis carbonization treatment time may be 0.5 to 6 hours, for example, 0.5 hour, 1 hour, 1.5 hours, 2 hours, 2.5 hours, 3 hours, 3.5 hours, 4 hours, 4.5 hours, 5 hours, 5.5 hours, or 6 hours, preferably 0.5 to 2 hours.
In some embodiments of the present application, the pyrolytic carbonization treatment may be performed in a pyrolysis apparatus. The pyrolysis apparatus may be any one of an atmosphere box furnace, a tube furnace, a rotary furnace and a pusher kiln. Preferably, the pyrolytic carbonization treatment is performed under an inert atmosphere. The inert atmosphere may be one or more of nitrogen, argon and helium.
In some embodiments, according to the second aspect, a third example of the second aspect is provided, wherein the pickling temperature is 30 to 60 ℃ and the pickling time is 30 to 60min.
During acid washing, the control of acid washing time and temperature is very important, and the loss of lithium-philic substances in the porous carbon material is easily caused by overlong acid washing time and overhigh acid washing temperature. In addition, the selection of the acid washing process parameters is also closely related to the addition amount of the lithium-philic chloride salt and the pore-forming agent.
After the pyrolysis carbonization treatment, the surface and the pores of the obtained carbon material contain lithium-philic substances, so the lithium-philic substances on the surface need to be removed by an acid washing process, thereby avoiding the surface lithium precipitation. In addition, impurities on the surface can be removed through an acid washing process, so that the reversible capacity in the charge-discharge cycle process is improved, and the lithium loss is reduced.
In some embodiments of the present application, the acid wash temperature may be 45-60 ℃; the pickling time can be 30-40min.
In some embodiments herein, the acid wash may be performed with one or more of hydrochloric acid, sulfuric acid, and nitric acid. In some embodiments, the acid wash may be performed with 5 to 15 wt.%, preferably 8 to 12 wt.% hydrochloric acid, with 5 to 15 wt.%, preferably 6 to 10 wt.% sulfuric acid, and with 3 to 10 wt.%, preferably 5 to 8 wt.% nitric acid.
In some embodiments of the present application, after pickling, washing and drying may be performed. The drying temperature can be 40-50 deg.C, and the drying time can be 5-8h. The cleaning may be performed with water.
In some embodiments, according to the second aspect, which proposes a fourth example of the second aspect, the curing process comprises: and (3) carrying out liquid curing treatment on the mixture, crushing the obtained massive solid, carrying out reinforced curing treatment, and crushing again to obtain the carbon precursor.
In the design, the dehydration and solidification effects can be further enhanced through crushing and strengthening solidification treatment, so that the composite resin structure is more stable.
In some embodiments herein, the resulting mixture may be left to defoam prior to being subjected to the liquid curing treatment. The standing time may be 0.5-2h, for example, 0.5h, 1h, 1.5h or 2h.
In some embodiments of the present application, the liquid curing process may be performed in an oven. During this process, the mixture solidifies into a solid mass with the solvent evaporating.
In some embodiments of the present application, after the liquid curing process, the resulting bulk solid may be broken into a powder by coarse breaking, fine breaking and milling, followed by an intensive curing process. The consolidation curing process may be performed in an oven. The dehydration and curing can be further enhanced by the enhanced curing treatment, so that the composite resin structure is more stable.
In some embodiments, according to the second aspect, there is provided a fifth example of the second aspect, wherein the temperature of the liquid curing process is 60 to 150 ℃. The temperature of the strengthening and curing treatment is 100-200 ℃.
In this design, the stability of the composite resin structure can be improved by optimizing the temperature of the liquid curing process and the strengthening curing process.
In some embodiments of the present application, the temperature of the liquid curing process may be 60-150 ℃, for example, 60 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃ or 150 ℃. The time for the liquid curing process decreases as the curing temperature increases. Alternatively, the time for the liquid curing treatment may be 1 to 8 hours, for example 4 to 6 hours.
In some embodiments of the present application, the temperature of the consolidation process may be 100-200 deg.C, such as 100 deg.C, 110 deg.C, 120 deg.C, 130 deg.C, 140 deg.C, 150 deg.C, 160 deg.C, 170 deg.C, 180 deg.C, 190 deg.C or 200 deg.C, and may preferably be 130-180 deg.C. The time for the intensive curing treatment decreases as the curing temperature increases. Alternatively, the time for the intensive curing treatment may be 30min to 4 hours, for example 2 to 4 hours.
In some embodiments of the present application, the consolidation process may be performed under an air, nitrogen, or argon atmosphere. The aeration rate of these gases may be 10-50mL/min.
In some embodiments of the present application, after the consolidation process, a re-crushing and sieving may be performed to obtain the carbon precursor. The obtained carbon precursor is micron-sized particles. The target size of the particles can be D10 is less than or equal to 5 μm, D50 is less than or equal to 10 μm, and D90 is less than or equal to 20 μm. And (3) carrying out pyrolysis carbonization treatment and acid washing on the granular carbon precursor to obtain the granular porous carbon material.
In some embodiments, according to the second aspect, a sixth example of the second aspect is provided, in which the obtained porous carbon material is surface-coated with graphite or resin, and after sintering, a coating layer is formed.
In the design, through optimizing the coating material, the electrolyte can be more effectively prevented from entering the porous carbon material, and the contact reaction of the electrolyte and the precipitated lithium alloy is avoided.
In some embodiments of the present application, the sintering temperature may be 800-1200 ℃, for example, may be 800 ℃, 900 ℃, 1000 ℃, 1100 ℃, or 1200 ℃.
In some embodiments, according to the second aspect, which proposes a seventh example of the second aspect, the lithium-philic chloride salt is one or more of zinc chloride, silver chloride, gold chloride, gallium chloride, indium chloride, and tin chloride.
After the pyrolysis carbonization treatment, the lithium-philic chloride salt is converted into corresponding metal simple substances and metal oxides. The metal simple substances and the metal oxides are lithium-philic substances, have lower nucleation overpotential, and can induce lithium metal to be precipitated in pores in the form of lithium alloy in the charging process. On the other hand, the lithium-philic chloride salt of the present invention also has a pore-forming function, but it is difficult to adjust the ratio of the mass of the lithium-philic substance in the pores to the volume of the pores to the above-mentioned range only by using the above-mentioned lithium-philic chloride salt as a pore-forming agent, and therefore, in order to more conveniently adjust the ratio of the mass of the lithium-philic substance in the pores to the volume of the pores, the present invention also particularly uses a pore-forming agent.
A third aspect of the present application provides a negative electrode sheet comprising the porous carbon material according to the first aspect of the present application or the porous carbon material obtained by the preparation method according to the second aspect of the present application.
In the technical solution of the embodiment of the present application, due to the adoption of the porous carbon material of the first aspect of the present application or the porous carbon material obtained by the preparation method of the second aspect of the present application, the negative electrode sheet of the present application has a high lithium storage space, a high compacted density and a high volumetric energy density.
The porous carbon material in the negative pole piece exists in a particle form.
The preparation method of the negative pole piece can comprise the following steps: and mixing the porous carbon material, the conductive agent, the binder and the solvent, coating the mixture on at least one surface of the negative current collector, and drying and cold-pressing the mixture to obtain the negative pole piece. The present application is not particularly limited with respect to the specific kinds of the conductive agent, the binder and the solvent, and the conductive agent, the binder and the solvent, which are generally used in the art for preparing the negative electrode sheet, may be used in the present application.
A fourth aspect of the present application provides a lithium ion battery comprising the negative electrode tab of the third aspect of the present application.
In the technical solution of the embodiment of the present application, due to the adoption of the porous carbon material of the first aspect of the present application or the porous carbon material obtained by the preparation method of the second aspect of the present application, the lithium ion battery of the present application has a high lithium storage space, a high compacted density and a high volumetric energy density.
The lithium ion battery of the present application includes: positive pole piece, the negative pole piece and the diaphragm of this application third aspect.
The positive pole piece includes: a positive electrode current collector and a positive electrode material layer coated on at least one surface of the positive electrode current collector. The preparation method of the positive pole piece comprises the following steps: and mixing the positive active substance, the binder and the conductive agent to form slurry, coating the slurry on at least one surface of the positive current collector, and drying and cold-pressing to obtain the positive pole piece.
The positive electrode active material is not particularly limited as long as it can accept and desorb lithium ions. In some embodiments of the present application, the positive active material may be selected from LiCoO 2 、LiMn 2 O 4 、LiFePO 4 、NCM(111/532/622/811/96)、LiNi 0.8 Co 0.15 Al 0.05 O 2 、LiNi 0.5 Mn 1.5 O 4 One or more of (a).
In some embodiments of the present application, the binder generally comprises a fluorinated polyolefin-based binder. The fluorinated polyolefin-based binder includes, but is not limited to, polyvinylidene fluoride (PVDF), modified derivatives thereof, and the like (e.g., modified with carboxylic acid, acrylic acid, and the like). In the positive electrode material layer, the binder itself has poor conductivity, and therefore the amount of the binder used cannot be excessively high. Preferably, the mass percentage of the binder in the positive electrode material layer is less than or equal to 2 wt% so as to obtain lower pole piece impedance.
In some embodiments of the present application, the conductive agent includes, but is not limited to, one or more of conductive carbon black, carbon fiber (VGCF), carbon Nanotube (CNT), and the like. The mass of the conductive agent may be 1 to 10 wt% of the total mass of the positive electrode material layer. More preferably, the weight ratio of the conductive agent to the positive active material in the positive electrode sheet is greater than or equal to 1.5.
The positive electrode current collector is generally a structure and a material that can collect current, and the specific kind thereof can be selected according to actual needs. In some embodiments of the present application, the positive electrode current collector includes, but is not limited to, a metal foil, and more particularly, may be a nickel foil or an aluminum foil.
In some embodiments of the present application, the separator includes, but is not limited to, one or more of polyethylene, polypropylene, polyvinylidene fluoride, polytetrafluoroethylene, polyacrylonitrile, polyimide, polyamide, polyester, and natural fibers.
The preparation method of the lithium ion battery comprises the following steps: cutting the positive pole piece, the diaphragm and the negative pole piece into target sizes, sequentially stacking or winding the positive pole piece, the diaphragm and the negative pole piece to the target sizes to prepare dry battery cores, and then injecting electrolyte to prepare the lithium ion battery.
After the lithium ion battery is charged, the lithium-philic substances in the porous carbon material holes have lower nucleation overpotential, so that lithium metal can be induced to be separated out in the holes in a lithium alloy mode, and the lithium metal simple substance is prevented from being separated out on the surface of a pole piece or on the surface of a coating layer of the porous carbon material, so that the loss caused by the contact reaction of the lithium metal and electrolyte is avoided.
A fifth aspect of the present application provides a battery module including the lithium ion battery of the fourth aspect of the present application.
In the technical solution of the embodiment of the present application, due to the use of the porous carbon material of the first aspect of the present application or the porous carbon material obtained by the preparation method of the second aspect of the present application, the battery module of the present application has a high lithium storage space, a high compacted density, and a high volumetric energy density.
A sixth aspect of the present application provides a battery pack including the battery module according to the sixth aspect of the present application.
In the technical solution of the embodiment of the present application, due to the use of the porous carbon material of the first aspect of the present application or the porous carbon material obtained by the preparation method of the second aspect of the present application, the battery pack of the present application has a high lithium storage space, a high compacted density, and a high volumetric energy density.
A seventh aspect of the present application provides an electric device including at least one of the lithium ion battery according to the fourth aspect of the present application, the battery module according to the fifth aspect of the present application, and the battery pack according to the sixth aspect of the present application.
In the technical solution of the embodiment of the present application, due to the use of the porous carbon material of the first aspect of the present application or the porous carbon material obtained by the preparation method according to the second aspect of the present application, the electric device of the present application has a high lithium storage space, a high compacted density and a high volumetric energy density.
The present application is further illustrated below with reference to examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present application.
Preparation of porous carbon Material
Example 1
Firstly, adding epoxy resin, lithium-philic chloride and pore-forming agent into ethanol (the amount of the ethanol is 100mL/500g of epoxy resin) according to a certain mass ratio, stirring, mixing and blending at the stirring speed of 1500r/min to obtain a uniform alcohol solution in which the epoxy resin and inorganic salt are dissolved, namely the prepared resin.
Then, the prepared resin is transferred into a ceramic crucible, kept stand for 1h for defoaming, and then placed in an oven for liquid curing treatment to obtain a blocky solid.
And then, after coarse crushing, fine crushing and powder grinding are carried out on the obtained blocky solid, the blocky solid is placed in an oven to be continuously subjected to reinforced curing treatment, and dehydration and curing are further reinforced, so that the structure of the composite resin is more stable.
And then, further carrying out secondary crushing and screening on the reinforced and cured large-particle composite resin to obtain micron-sized particles with a certain size, and preparing the micron-sized particles into a brown black carbon precursor.
And then, carrying out pyrolysis carbonization treatment on the brown black carbon precursor at high temperature, and further removing impurities, demagnetizing and grading to obtain the porous carbon material.
After that, the porous carbon material is acid-washed with an inorganic acid of a certain concentration. After acid washing, filtering is carried out while fully washing with deionized water, and washing is carried out for three times, wherein the washing time is respectively 10min, 10min and 5min. The filter cake was dried in an oven at 45 ℃ for 5h.
And finally, coating the porous carbon material with a coating material, and sintering at 1000 ℃ to form a coating layer.
The specific parameters in this example are detailed in tables 1 and 2 below.
The surface morphology of the porous carbon material was observed by scanning electron microscopy (SEM, femina), as shown in fig. 1.
The smooth cross-section of the porous carbon material was prepared using an ion polisher (CP) and the cross-sectional morphology was observed using a scanning electron microscope (SEM, femina) as shown in fig. 2.
Example 2 to example 23
Porous carbon materials of examples 2 to 23 were prepared as described in example 1, except that the parameters listed in tables 1 and 2 below were different from example 1.
Comparative examples 1 to 5
Porous carbon materials of comparative examples 1 to 5 were prepared according to the method described in example 1, except that the parameters listed in tables 1 and 2 below were different from example 1.
TABLE 1
Lithium ion batteries were prepared according to the following general preparation method using the porous carbon materials prepared in examples 1 to 23 and comparative examples 1 to 5.
Preparation of lithium ion batteries
Preparing a negative pole piece:
the prepared porous carbon material is respectively and fully stirred and uniformly mixed with acetylene black serving as a conductive agent and polyvinylidene fluoride (PVDF) serving as a binder in an N-methyl pyrrolidone solvent system according to a weight ratio of 94 -2 . Cutting into corresponding size for use.
Preparing a positive pole piece:
LiNi serving as a positive electrode active material 0.8 Co 0.1 Mn 0.1 O 2 (NCM 811), acetylene black as a conductive agent and PVDF as a binder are mixed according to a mass ratio of 96; the positive electrode slurry is evenly coated on a positive electrode current collector aluminum foil with the thickness of 12 mu m, and the positive electrode surface capacity is 3.5mAh & cm -2 . Air-drying at room temperature, transferring to 50 deg.C oven, and continuously drying for 5 hrAnd cutting into corresponding sizes for later use.
Assembling the lithium ion battery:
cutting the positive pole piece, the diaphragm and the negative pole piece into target sizes, sequentially stacking or winding the positive pole piece, the diaphragm and the negative pole piece to the target sizes to prepare dry battery cores, and then injecting electrolyte to prepare the lithium ion battery. In the electrolyte, a solvent is a mixture of ethylene carbonate EC, ethyl methyl carbonate EMC and dimethyl carbonate DMC (mass ratio is 1; the lithium salt is LiFSI with the concentration of 1mol/L. And (5) injecting liquid, carrying out vacuum packaging, and standing for infiltration. And then the lithium ion battery is obtained through the processes of formation, standing and the like.
Characterization of porous carbon materials after lithium precipitation
The lithium ion battery comprising the porous carbon material of example 1 was charged to precipitate lithium metal as a lithium alloy in the pores. And disassembling the battery to obtain the porous carbon material containing the lithium alloy. And preparing the smooth section of the porous carbon material by using an ion polisher. The appearance of the smooth section was observed by scanning electron microscopy as shown in FIG. 3.
The obtained porous carbon material containing a lithium alloy was subjected to surface scanning by an energy dispersive X-ray spectrometer (EDS) equipped with a scanning electron microscope to characterize the distribution of cross-sectional elements (important elements such as Zn, ag, sn, etc. in the lithium-philic substance), as shown in fig. 5.
Characterization of porous carbon materials after delithiation
A lithium ion battery comprising the porous carbon material of example 1 was charged and then discharged. And (5) disassembling the battery to obtain the porous carbon material after lithium removal. And preparing the smooth section of the porous carbon material by using an ion polisher. The appearance of the smooth section was observed by scanning electron microscopy as shown in FIG. 4.
The cross-sectional element (important elements such as Zn, ag, sn, etc. in the lithium-philic substance) distribution characterization of the obtained porous carbon material after lithium removal is performed by using an energy dispersive X-ray spectrometer (EDS) equipped with a scanning electron microscope for surface scanning, as shown in fig. 6.
Electrical Performance testing
1. Charge and discharge cycle test
Performing charge-discharge cycle test by using an electrochemical workstation, and performing 1.5 mA-cm on the prepared lithium ion battery at 25 DEG C -2 Is charged to 4.3V and then charged at a constant voltage of 4.3V until the current drops to 0.3mA cm -2 (ii) a Then 1.5mA cm -2 Is discharged to 3.0V. The test results are shown in table 3 below, based on the 80% decay in discharge capacity at the first week.
2. First week efficiency test
The prepared lithium ion battery is heated at 25 ℃ and is heated at 1.5 mA-cm -2 Is charged to 4.3V and then charged at a constant voltage of 4.3V until the current drops to 0.3mA cm -2 Obtaining first cycle charging specific capacity (Cc 1); then 1.5mA cm -2 The constant current is discharged to 3.0V to obtain the first-cycle discharge specific capacity (Cd 1), and the first-cycle efficiency of the lithium ion battery is calculated according to the following formula. First cycle efficiency of the lithium ion battery = first cycle specific discharge capacity (Cd 1)/first cycle specific charge capacity (Cc 1). The test results are shown in table 3 below.
CB value
The ratio of the negative electrode surface capacity to the positive electrode surface capacity is CB value, and the negative electrode surface capacity used in the application is 2.1mAh & cm -2 The capacity of the anode and the cathode is 3.5mAh cm -2 The ratio was 0.6, i.e., the CB value was 0.6.
4. Energy density test
At constant voltage (4.3V of the invention), the first cycle discharge capacity (Ah) is multiplied by the ratio of discharge voltage to cell mass. That is, the energy density = first-week discharge capacity (Ah) × discharge voltage (4.3V)/cell mass (kg).
5. Cell expansion ratio test
Measuring thickness L before testing electric core 0 Standing at 25 deg.C for 5min, charging to 4.3V at 1/3C, constant voltage charging to current 0.05mA at 4.3V, standing for 5min, discharging to 2.8V at 1/3C, standing for 5min, charging to 4.3V at 1/3C, constant voltage charging to current 0.05mA at 4.3V, and recording cell thickness L 1 Calculating the swelling DeltaL = L 1 -L 0 The expansion rate is eta = [ Delta ] L/L 1 。
As can be seen by comparing example 1 with comparative example 1, comparative example 1 has no lithium-philic substance ZnCl added and no coating layer formed, and comparative example 1 has significantly lower cycle life and first cycle efficiency than example 1, but significantly higher cell first cycle expansion than example 1. Therefore, the addition of the lithium-philic substance and the coating layer have significant effects on the cycle life, the first-week efficiency and the first-week expansion rate of the battery cell.
It can be seen by comparing example 1 with comparative example 2 that comparative example 2 does not add the lithium-philic substance ZnCl, the cycle life and first-cycle efficiency of comparative example 2 are significantly lower than example 1, but the first-cycle expansion rate of the cell is significantly higher than example 1. Therefore, the addition of the lithium-philic substance has a significant effect on the cycle life, the first-week efficiency and the first-week expansion rate of the cell.
As can be seen by comparing example 1 and comparative example 3, comparative example 3 does not form a coating layer, and comparative example 3 has significantly lower cycle life and first-cycle efficiency than example 1, but significantly higher cell first-cycle expansion rate than example 1. It can be seen that the coating layer has a significant effect on cycle life, first cycle efficiency and first cycle expansion rate of the cell.
As can be seen by comparing example 1 with comparative examples 4 to 5, the mass ratio of the lithium-philic substance and the porous carbon material of comparative examples 4 and 5 is out of the range of the present application, and the cycle life and the first-week efficiency of comparative examples 4 and 5 are significantly lower than those of example 1, but the first-week expansion rate of the cell is significantly higher than that of example 1. Therefore, the mass ratio of the lithium-philic substance and the porous carbon material has a significant influence on the cycle life, the first-cycle efficiency and the first-cycle expansion rate of the battery cell.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the appended claims.
Claims (20)
1. A porous carbon material characterized in that the porous carbon material has pores inside, and a lithium-philic substance is included in the pores;
the ratio of the mass of the lithium-philic substance to the volume of the holes is 3:1-32;
and a coating layer is arranged on the surface of the porous carbon material.
2. The porous carbon material according to claim 1, wherein the ratio of the mass of the lithium-philic substance to the volume of the pores is 10.
3. Porous carbon material according to claim 1 or 2, wherein the lithium-philic substance is one or more of the metals Zn, ag, au, ga, in, sn and oxides thereof.
4. Porous carbon material according to claim 1 or 2, wherein the coating layer has a thickness of 50-350nm.
5. Porous carbon material according to claim 1 or 2, characterized in that the pore size of the pores is 0.1-10 μm.
6. The porous carbon material according to claim 1 or 2, wherein the mass ratio of the lithium-philic substance to the porous carbon material is 9:1-1.5.
7. The porous carbon material according to claim 1 or 2, wherein the porous carbon material is in the form of particles, and the particle size of the particulate porous carbon material is 5 to 30 μm.
8. A method for producing a porous carbon material, comprising:
mixing resin, lithium-philic chloride salt, a pore-forming agent and a solvent to obtain a mixture;
curing the mixture to obtain a carbon precursor;
carrying out pyrolysis carbonization treatment on the carbon precursor, and after acid washing, obtaining a porous carbon material; and
the obtained porous carbon material is surface-coated to form a coating layer.
9. The method of claim 8, wherein the ratio of the mass of the resin to the total mass of the lithium-philic chloride salt and the pore former is 1:1-1.
10. The method according to claim 8 or 9, wherein the pyrolysis carbonization treatment is performed at a temperature of 600 ℃ to 1200 ℃ for 0.5 to 6 hours.
11. The method according to claim 8 or 9, wherein the pickling temperature is 30 to 60 ℃ and the pickling time is 30 to 60min.
12. The production method according to claim 8 or 9,
the curing treatment comprises: and carrying out liquid curing treatment on the mixture, crushing the obtained massive solid, carrying out reinforced curing treatment, and crushing again to obtain the carbon precursor.
13. The method for preparing the resin composition according to claim 12, wherein the temperature of the liquid curing treatment is 60 to 150 ℃;
the temperature of the strengthening and curing treatment is 100-200 ℃.
14. The production method according to claim 8 or 9, wherein the obtained porous carbon material is surface-coated with graphite or resin, and after sintering, a coating layer is formed.
15. The method according to claim 8 or 9, wherein the lithium-philic chloride salt is one or more of zinc chloride, silver chloride, gold chloride, gallium chloride, indium chloride and tin chloride.
16. A negative electrode sheet comprising the porous carbon material according to any one of claims 1 to 7 or the porous carbon material obtained by the production method according to any one of claims 8 to 15.
17. A lithium ion battery comprising the negative electrode sheet of claim 16.
18. A battery module comprising the lithium ion battery of claim 17.
19. A battery pack comprising the battery module according to claim 18.
20. An electric device comprising at least one of the lithium ion battery of claim 17, the battery module of claim 18, and the battery pack of claim 19.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107994207A (en) * | 2016-10-26 | 2018-05-04 | 宁德时代新能源科技股份有限公司 | Lithium ion battery and cathode plate thereof |
| WO2018107743A1 (en) * | 2016-12-15 | 2018-06-21 | 宁德时代新能源科技股份有限公司 | Positive pole piece of lithium ion battery, preparation method therefor and battery using same |
| CN114400302A (en) * | 2021-02-10 | 2022-04-26 | 北京卫蓝新能源科技有限公司 | Porous carbon microsphere, preparation method thereof, carbon-lithium composite material, negative electrode and lithium metal battery |
| CN114447325A (en) * | 2020-11-02 | 2022-05-06 | 北京卫国创芯科技有限公司 | Porous carbon material, preparation method thereof, negative electrode and lithium metal battery |
| CN114447329A (en) * | 2020-11-02 | 2022-05-06 | 北京卫国创芯科技有限公司 | Porous carbon material and preparation method and application thereof |
-
2022
- 2022-07-12 CN CN202210816768.0A patent/CN115838163A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107994207A (en) * | 2016-10-26 | 2018-05-04 | 宁德时代新能源科技股份有限公司 | Lithium ion battery and cathode plate thereof |
| WO2018107743A1 (en) * | 2016-12-15 | 2018-06-21 | 宁德时代新能源科技股份有限公司 | Positive pole piece of lithium ion battery, preparation method therefor and battery using same |
| CN114447325A (en) * | 2020-11-02 | 2022-05-06 | 北京卫国创芯科技有限公司 | Porous carbon material, preparation method thereof, negative electrode and lithium metal battery |
| CN114447329A (en) * | 2020-11-02 | 2022-05-06 | 北京卫国创芯科技有限公司 | Porous carbon material and preparation method and application thereof |
| CN114400302A (en) * | 2021-02-10 | 2022-04-26 | 北京卫蓝新能源科技有限公司 | Porous carbon microsphere, preparation method thereof, carbon-lithium composite material, negative electrode and lithium metal battery |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116443847A (en) * | 2023-04-18 | 2023-07-18 | 四川坤天新能源科技有限公司 | Metal oxide doped hard carbon composite material and preparation method thereof |
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