Carbon nanomaterial in-situ modified lithium salt solid waste powder and preparation method thereof

Abstract

The present application relates to the technical field of multifunctional building materials, and discloses a kind of carbon nanomaterial in-situ modified lithium salt solid waste powder and preparation method thereof, greatly reduce the energy barrier of amorphous carbon atom conversion into graphene, promote the conversion of graphene, and more amorphous Al2O3 can be generated in high-temperature treatment process;After modified lithium salt solid waste replaces part of cement, the rate of lithium salt solid waste powder participating in hydration reaction is fast, graphene and lithium salt solid waste powder produce synergistic hydration reaction, based on the template arrangement effect of graphene grown in-situ, under the promotion of lithium ion in lithium salt solid waste, the secondary hydration product produced by modified lithium salt solid waste is regularly and densely arranged in cement stone pore, which significantly reduces the porosity of cement stone;Graphene and amorphous Al2O3 produce synergistic effect, promote the formation of low-carbon hydrated calcium aluminate carbonate and other semi-carbonate products in hydration product, help to stabilize the crystal structure of AFt phase hydration product, and ensure the development of cement stone mechanical properties and stability.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of multifunctional building materials, and particularly relates to lithium salt solid waste powder in-situ modified by carbon nanomaterials and a preparation method thereof. BACKGROUND

[0002] With the continuous expansion of the application field of lithium salt and the rapid growth of market demand, the lithium salt industry in China has developed rapidly, and a large amount of industrial by-products has been produced. Lithium salt solid waste powder is obtained based on nitric acid pressure leaching technology, and the lithium salt solid waste powder has pozzolanic activity and can be used as an admixture and auxiliary cementitious material in the building material industry. Compared with lithium residue obtained by sulfuric acid leaching, the lithium salt solid waste powder has obvious advantages. For example, lithium residue obtained by concentrated sulfuric acid leaching in Chinese patent application No. CN201711444186.X will cause concrete to expand and crack when added to concrete due to excessive SO3.

[0003] Carbon nanomaterials can improve the activity of lithium salt solid waste powder in cement by regulating hydration reaction, improving pore structure, and improving interface bonding. For example, graphene in Chinese patent application No. CN201310098143.6 needs to be pretreated by surface modification, ultrasonic dispersion, and water reducing agent dispersion before being added to cement. However, the pretreated carbon nanomaterials still have problems such as poor overall effect of surface modification and agglomeration. Therefore, a method of in-situ growth is needed to achieve the most sufficient combination and dispersion of carbon nanomaterials with lithium salt solid waste powder. SUMMARY

[0004] Based on the above problems, the present application provides lithium salt solid waste powder in-situ modified by carbon nanomaterials and a preparation method thereof. Graphene and lithium salt solid waste powder produce a synergistic hydration reaction. Graphene in-situ grown has a template arrangement effect. Under the promotion of lithium ions in lithium salt solid waste, the secondary hydration products produced by the modified lithium salt solid waste powder are regularly and densely arranged in the cement stone pores, thereby reducing the porosity of the cement stone. In addition, graphene and amorphous Al2O3 produce a synergistic effect, which can promote the formation of hemicalcium salt products in the hydration products, thereby helping to stabilize the crystal structure of the AFt phase hydration product, and having a positive effect on further ensuring the development of the mechanical properties and stability of the cement stone.

[0005] To achieve the above technical effects, the technical solution adopted by the present application is as follows:

[0006] A preparation method of lithium salt solid waste powder in-situ modified by carbon nanomaterials, comprising:

[0007] Mixing lithium salt solid waste powder, a carbon source, and an iron salt catalyst and stirring uniformly with water to obtain a mixed wet material; the lithium salt solid waste powder is a solid waste powder obtained after treating lithium salt minerals based on nitric acid pressure technology;

[0008] The mixed wet material is dried, and then the dried mixture is calcined under the condition of inert gas atmosphere, the calcination temperature is 600 DEG C-900 DEG C, the calcination time is 3h-9h, and then cooled to room temperature to obtain the carbon nanomaterial in-situ modified lithium salt solid waste powder.

[0009] Further, the lithium salt solid waste powder comprises the following mass fraction of chemical composition:

[0010] SiO2 70%~75%;

[0011] Al2O3 20%~25%;

[0012] Impurity oxide 0%~5%;

[0013] Among them, the impurity oxide is one or a combination of multiple oxides of Fe2O3, K2O, CaO and MgO.

[0014] Further, the carbon source is one of anhydrous glucose, sucrose or corn straw, and the mass of the carbon source is 4%-16% of the total mass of the carbon source and the lithium salt solid waste powder.

[0015] Further, the iron salt catalyst is ferric nitrate or ferric chloride, and the mass of the iron salt catalyst is 20%-80% of the mass of the carbon source.

[0016] Further, the lithium salt solid waste powder, the carbon source and the iron salt catalyst are mixed and stirred with water until uniform, and the stirring time is 6h-24h.

[0017] To achieve the above technical effects, the application further provides a carbon nanomaterial in-situ modified lithium salt solid waste powder, which is prepared by the preparation method of the carbon nanomaterial in-situ modified lithium salt solid waste powder.

[0018] Compared with the prior art, the application has the following beneficial effects:

[0019] 1. The lithium salt solid waste powder is a solid waste powder obtained based on nitric acid pressurization technology, has pozzolanic activity, and can participate in the hydration reaction of cement; the lithium salt solid waste powder is used as an auxiliary cementing material to replace part of the cement, and the residual Li +The participation in the hydration reaction of cement, the reaction with silicate minerals in cement to form lithium silicate, can regulate the microstructure of C-S-H gel, make it densification, and improve the mechanical properties of cement stone. Moreover, with the extension of hydration time, the silicon-oxygen bond and aluminum-oxygen bond in lithium salt solid waste powder begin to break, and at the same time, the calcium hydroxide in the cement hydration product reacts to form hydrated silicate gel and hydrated calcium aluminate, the silicon dioxide in the lithium salt solid waste powder will reduce the Ca / Si molar ratio of the main hydration product C-S-H gel, and will increase the length of the silicon chain; the aluminum oxide in the lithium salt solid waste powder can introduce more Al elements into the C-S-H gel, thereby forming C-A-S-H with a tobermorite structure, which helps to improve the strength of the cement stone. Therefore, in this embodiment, not only the consumption of natural resources and energy is reduced, and CO2 emission is reduced, but also the utilization of industrial solid waste is realized; moreover, compared with the solid waste lithium residue obtained by ordinary sulfuric acid method, there is no excess sulfate, and the problem of concrete cracking and expansion caused by the reaction of sulfate and calcium ions is avoided.

[0020] 2. The lithium salt solid waste powder particles have a porous feature, under the action of van der Waals force, the carbon source and the iron salt catalyst are adsorbed together with the lithium salt solid waste powder in water; under high temperature, the carbon atoms after decomposition of the carbon source and the iron salt catalyst react to form reduced iron, which can be adsorbed on the surface of the lithium salt solid waste powder, greatly reducing the energy barrier of the conversion of amorphous carbon atoms into graphene, and promoting the conversion of graphene. At the same time, the lithium salt solid waste powder can be converted into more amorphous Al2O3 under high temperature, so that the rate of participation in the hydration reaction of the lithium salt solid waste powder is accelerated. Graphene and lithium salt solid waste powder produce a synergistic hydration reaction, and the in-situ grown graphene has a template arrangement effect, so that the secondary hydration products produced by the modified lithium salt solid waste powder are regularly and densely arranged in the pores of the cement stone, and under the promotion of lithium ions in the lithium salt solid waste, the porosity of the cement stone is significantly reduced; in addition, the graphene and amorphous Al2O3 produce a synergistic effect, which can promote the formation of hemi-carbonate products in the hydration product, thereby helping to stabilize the crystal structure of the AFt phase hydration product, and having a positive effect on further ensuring the development of the mechanical properties and stability of the cement stone. BRIEF DESCRIPTION OF DRAWINGS

[0021] Figure 1 The SEM picture of the unmodified lithium salt solid waste.

[0022] Figure 2 The SEM picture of the in-situ modified lithium salt solid waste in Example 2.

[0023] Figure 3 The XRD comparison chart of the synthesis sample of Example 4, commercial graphene, and unmodified lithium salt solid waste.

[0024] Figure 4Raman spectrum comparison chart of the sample synthesized in Example 4, commercial graphene, and unmodified lithium salt solid waste. DETAILED DESCRIPTION

[0025] In order to make the objectives, technical solutions and advantages of the present application clearer, the present application is further described in detail below with reference to the embodiments and drawings, the illustrative embodiments of the present application and the description thereof are only used to explain the present application, and do not limit the present application.

[0026] Example 1

[0027] The method for preparing the lithium salt solid waste powder in-situ modified by the carbon nanomaterial comprises the following steps:

[0028] The lithium salt solid waste powder, the carbon source and the iron salt catalyst are mixed and stirred uniformly with water to obtain mixed wet materials; the lithium salt solid waste powder is the solid waste powder obtained after the lithium salt mineral is treated based on the nitric acid pressurization technology;

[0029] The mixed wet materials are dried, and then the dried mixture is calcined under the condition of the atmosphere of inert gas, the calcination temperature is 600-900 DEG C, the calcination time is 3-9 h, and then the mixture is cooled to room temperature to obtain the lithium salt solid waste powder in-situ modified by the carbon nanomaterial.

[0030] The lithium salt solid waste powder is the solid waste powder obtained based on the nitric acid pressurization technology, has the pozzolanic activity, and can participate in the hydration reaction of cement; the lithium salt solid waste powder is used as an auxiliary cementitious material to replace part of the cement, the residual Li +Participating in the hydration reaction of cement, reacting with silicate minerals in cement to form lithium silicate, can regulate the microstructure of C-S-H gel, make it densification, and improve the mechanical properties of cement stone. Moreover, with the extension of hydration time, the silicon-oxygen bond and aluminum-oxygen bond in lithium salt solid waste powder begin to break, and at the same time, the calcium hydroxide in the cement hydration product reacts to form hydrated silicate gel and hydrated calcium aluminate, the silicon dioxide in lithium salt solid waste powder will reduce the Ca / Si molar ratio of C-S-H gel, the main hydration product, and will increase the length of its silicon chain; The alumina in lithium salt solid waste powder can introduce more Al elements into C-S-H gel, thereby forming C-A-S-H with a tobermorite structure, which helps to improve the strength of the cement stone. Therefore, in this embodiment, not only the consumption of natural resources and energy is reduced, and CO2 emission is reduced, but also the utilization of industrial solid waste is realized; Moreover, compared with the solid waste lithium residue obtained by the ordinary sulfuric acid method, there is no excess sulfate, which avoids the problem of concrete cracking and expansion caused by the reaction of sulfate and calcium ions. In this embodiment, the lithium salt solid waste powder particles have porous characteristics, and under the action of van der Waals force, the carbon source and iron salt catalyst are adsorbed together with the lithium salt solid waste powder in water; At high temperature, the carbon atoms after the decomposition of the carbon source and the iron salt catalyst react to form reduced iron, which can be adsorbed on the surface of the lithium salt solid waste powder, greatly reducing the energy barrier of the conversion of amorphous carbon atoms into graphene, and promoting the conversion of graphene. At the same time, the lithium salt solid waste powder can be converted into more amorphous Al2O3 under high temperature treatment, so that the rate of lithium salt solid waste powder participating in the hydration reaction is accelerated. Graphene and lithium salt solid waste powder produce a synergistic hydration reaction, and the in-situ grown graphene has a template arrangement effect, so that the secondary hydration products produced by the modified lithium salt solid waste powder are regularly and densely arranged in the pores of the cement stone. In addition, lithium ions in the lithium salt solid waste continuously insert and deintercalate between the layers during the growth of graphene, resulting in defect sites between the layers of graphene, which further induces the deposition of cement hydration products at the defect sites, enhances the template rearrangement effect of graphene on cement hydration products, and significantly reduces the porosity of the cement stone; In addition, the synergistic effect of graphene and amorphous Al2O3 can promote the formation of low-carbon hydrated calcium aluminate and other semi-carbonate products in the hydration product, thereby helping to stabilize the crystal structure of the AFt phase hydration product, which has a positive effect on further ensuring the development of the mechanical properties and stability of the cement stone.

[0031] It should be noted that in this embodiment, the carbon source, iron salt catalyst and lithium salt solid waste powder are uniformly mixed in water to achieve molecular-level mixing, avoiding chemical modification, ultrasonic dispersion and other processes during the dispersion of nanomaterials, and ensuring the most sufficient dispersion of carbon nanomaterials.

[0032] Example 2

[0033] A method for preparing a lithium salt solid waste powder modified in-situ by a carbon nanomaterial, comprising:

[0034] Step 1, lithium salt solid waste powder, anhydrous glucose and iron nitrate nine water were mixed with appropriate amount of water for 6h, so that they were mixed uniformly; the mass of anhydrous glucose accounted for 2% of the total mass of anhydrous glucose and lithium salt solid waste powder, and the mass of iron salt catalyst was 50% of the mass of anhydrous glucose.

[0035] Step 2, after the mixture in step 1 was fully stirred and uniform, it was placed in a forced air drying oven for drying.

[0036] Step 3, the mixture after drying in step 2 was placed in a tube furnace and calcined at high temperature under inert atmosphere, the temperature was kept at 700℃ for 4h, and after natural cooling to room temperature, the calcined sample was taken out of the tube furnace.

[0037] Step 4, the calcined mixture was replaced with 30% cement, and 20mm neat paste cubic test blocks and 40mmx40mmx160mm mortar test blocks were prepared according to the standard for testing mechanical properties, with a water-cement ratio of 0.5 and standard curing for 28 days.

[0038] Example 3

[0039] Step 1, lithium salt solid waste powder, anhydrous glucose and iron nitrate nine water were mixed with appropriate amount of water for 6h, so that they were mixed uniformly; the mass of anhydrous glucose accounted for 2% of the total mass of anhydrous glucose and lithium salt solid waste powder, and the mass of iron salt catalyst was 50% of the mass of anhydrous glucose.

[0040] Step 2, after the mixture in step 1 was fully stirred and uniform, it was placed in a forced air drying oven for drying.

[0041] Step 3, the mixture after drying in step 2 was placed in a tube furnace and calcined at high temperature under inert atmosphere, the temperature was kept at 700℃ for 4h, and after natural cooling to room temperature, the calcined sample was taken out of the tube furnace.

[0042] Step 4, the calcined mixture was replaced with 30% cement, and 20mm neat paste cubic test blocks and 40mmx40mmx160mm mortar test blocks were prepared according to the standard for testing mechanical properties, with a water-cement ratio of 0.5 and standard curing for 28 days.

[0043] Example 4

[0044] Step 1, lithium salt solid waste powder, anhydrous glucose and iron nitrate nine water were mixed with appropriate amount of water for 6h, so that they were mixed uniformly; the mass of anhydrous glucose accounted for 2% of the total mass of anhydrous glucose and lithium salt solid waste powder, and the mass of iron salt catalyst was 50% of the mass of anhydrous glucose.

[0045] Step 2, after the mixture in step 1 was fully stirred and uniform, it was placed in a forced air drying oven for drying.

[0046] Step 3, the mixture after drying in step 2 is put into a tube furnace, calcined at high temperature under inert atmosphere, the temperature is kept at 700℃, the temperature is kept for 4h, after natural cooling to room temperature, the sample after calcination is taken out of the tube furnace.

[0047] Step 4, the mixture after calcination is replaced by 30% cement, 20mm neat paste cubic test block and 40mm*40mm*160mm mortar test block are prepared according to the standard for testing mechanical properties, the water-cement ratio is 0.5, and the standard curing is kept for 28 days.

[0048] Example 5

[0049] Step 1, lithium salt solid waste powder, anhydrous glucose and iron nitrate nonahydrate are stirred and mixed with appropriate amount of water for 6h to make them uniformly mixed; the mass of anhydrous glucose accounts for 4% of the total mass of anhydrous glucose and lithium salt solid waste powder, and the mass of iron nitrate nonahydrate is 50% of the mass of anhydrous glucose.

[0050] Step 2, the mixture after sufficient stirring in step 1 is put into a forced air drying oven for drying.

[0051] Step 3, the mixture after drying in step 2 is put into a tube furnace, calcined at high temperature under inert atmosphere, the temperature is kept at 700℃, the temperature is kept for 6h, after natural cooling to room temperature, the sample after calcination is taken out of the tube furnace.

[0052] Step 4, the mixture after calcination is replaced by 30% cement, 20mm neat paste cubic test block and 40mm*40mm*160mm mortar test block are prepared according to the standard for testing mechanical properties, the water-cement ratio is 0.5, and the standard curing is kept for 28 days.

[0053] Example 6

[0054] Step 1, lithium salt solid waste powder, anhydrous glucose and iron nitrate nonahydrate are stirred and mixed with appropriate amount of water for 6h to make them uniformly mixed; the mass of anhydrous glucose accounts for 4% of the total mass of anhydrous glucose and lithium salt solid waste powder, and the mass of iron nitrate nonahydrate is 50% of the mass of anhydrous glucose.

[0055] Step 2, the mixture after sufficient stirring in step 1 is put into a forced air drying oven for drying.

[0056] Step 3, the mixture after drying in step 2 is put into a tube furnace, calcined at high temperature under inert atmosphere, the temperature is kept at 700℃, the temperature is kept for 4h, after natural cooling to room temperature, the sample after calcination is taken out of the tube furnace.

[0057] Step 4, the mixture after calcination is replaced by 30% cement, 20mm neat paste cubic test block and 40mm*40mm*160mm mortar test block are prepared according to the standard for testing mechanical properties, the water-cement ratio is 0.5, and the standard curing is kept for 28 days.

[0058] Example 7

[0059] Step 1, lithium salt solid waste powder, corn straw and iron nitrate nine water were mixed with appropriate amount of water for 6h, so that they were mixed uniformly; the mass of anhydrous glucose accounted for 4% of the total mass of anhydrous glucose and lithium salt solid waste powder, and the mass of iron nitrate nine water was 50% of the mass of anhydrous glucose.

[0060] Step 2, after the mixture in step 1 was fully stirred and uniform, it was placed in a forced air drying oven for drying.

[0061] Step 3, the mixture after drying in step 2 was placed in a tube furnace and calcined at high temperature under inert atmosphere, the temperature was kept at 600℃ for 4h, and after natural cooling to room temperature, the calcined sample was taken out of the tube furnace.

[0062] Step 4, the calcined mixture was replaced with 30% cement, and 20mm neat paste cubic test blocks and 40mm×40mm×160mm mortar test blocks were prepared according to the standard for testing mechanical properties, with a water-cement ratio of 0.5 and standard curing for 28 days.

[0063] Example 8

[0064] Step 1, lithium salt solid waste powder, anhydrous glucose and iron nitrate nine water were mixed with appropriate amount of water for 6h, so that they were mixed uniformly; the mass of anhydrous glucose accounted for 4% of the total mass of anhydrous glucose and lithium salt solid waste powder, and the mass of iron nitrate nine water was 50% of the mass of anhydrous glucose.

[0065] Step 2, after the mixture in step 1 was fully stirred and uniform, it was placed in a forced air drying oven for drying.

[0066] Step 3, the mixture after drying in step 2 was placed in a tube furnace and calcined at high temperature under inert atmosphere, the temperature was kept at 800℃ for 4h, and after natural cooling to room temperature, the calcined sample was taken out of the tube furnace.

[0067] Step 4, the calcined mixture was replaced with 30% cement, and 20mm neat paste cubic test blocks and 40mm×40mm×160mm mortar test blocks were prepared according to the standard for testing mechanical properties, with a water-cement ratio of 0.5 and standard curing for 28 days.

[0068] Comparative Example

[0069] Step 1, lithium salt solid waste powder was placed in a tube furnace and calcined at high temperature under inert atmosphere, the temperature was kept at 700℃ for 4h, and after natural cooling to room temperature, the calcined sample was taken out of the tube furnace.

[0070] Step 2: The mixture after calcination is replaced with 30% cement to prepare 20mm neat paste cubic test blocks and 40mmx40mmx160mm mortar test blocks according to the standard for testing mechanical properties, with a water-cement ratio of 0.5, and standard curing for 28 days.

[0071] The compressive strength of the neat paste cubic test blocks and the flexural strength of the mortar test blocks in Examples 2-4 and the control example are measured respectively, and the relevant data are shown in Tables 1 and 2:

[0072] Table 1: Compressive strength data table of neat paste test blocks

[0073] Example Test block size Compressive strength Curing time Example 2 20 mm 3 ]] 15.75 28 Example 3 20 mm 3 ]] 18.21 28 Example 4 20 mm 3 ]] 14.98 28 Control Example 20 mm 3 ]] 14.91 28

[0074] Table 2: Flexural strength data table of mortar test blocks

[0075] Example Test block size Flexural strength Curing time Example 2 40 x 40 x 160 mm 3 ]] 10.93 28 Example 3 40 x 40 x 160 mm 3 ]] 12.62 28 Example 4 40 x 40 x 160 mm 3 ]] 9.84 28 Control Example 40 x 40 x 160 mm 3 ]] 9.6 28

[0076] As can be seen from the above tables, different glucose proportions increase the 30d neat paste compressive strength by 0%-28%, and increase the 30d mortar flexural strength by 0%-13%, with 4% glucose proportion having the largest mechanical property improvement.

[0077] The lithium salt solid waste powder modified in situ by the carbon nanomaterial prepared in Example 4 and the control example is characterized by SEM, XRD and Raman spectroscopy. Figure 1 is the SEM image of the lithium salt solid waste before treatment, Figure 2 is the SEM image of the lithium salt solid waste modified in situ in Example 4; Figure 3 is the XRD comparison picture of the synthetic sample in Example 4, commercial graphene and unmodified lithium salt solid waste, and the XRD curve of the modified lithium salt solid waste is enhanced at about 26°, and the graphene characteristic peak is about 26°; Figure 4 is the Raman spectrum comparison chart of the synthetic sample in Example 4, commercial graphene and unmodified lithium salt solid waste, and the three characteristic Raman peaks of graphene are at 1350cm -1 , 1580cm -1 and 2680cm -1 , and the lithium salt solid waste has no peak at these three places, and the modified lithium salt solid waste has the characteristic peaks of graphene at these three places.

[0078] This method uses low-cost anhydrous glucose as a raw material for preparing carbon nanomaterials to realize in-situ modification of lithium salt solid waste powder. From the perspective of solving scientific problems, this method solves the problem of dispersion of carbon nanomaterials in lithium salt solid waste powder. From the perspective of preparation process, it overcomes the cumbersome chemical modification and physical ultrasonic dispersion process of carbon nanomaterials. From the economic point of view, the cost of raw materials is lower than that of commercially available carbon nanomaterials.

[0079] The above is an embodiment of the present application. The above embodiment and specific parameters in the embodiment are only for clearly describing the verification process of the application and are not intended to limit the patent protection scope of the application. The patent protection scope of the application is still subject to the claims, and any equivalent structural changes made by referring to the content of the specification and drawings of the application should also be included in the protection scope of the application.

Claims

1. A method for preparing a lithium salt solid waste powder in which carbon nanomaterials are modified in situ, characterized by, The application relates to a carbon nanomaterial in-situ modified lithium salt solid waste powder and a preparation method thereof. The lithium salt solid waste powder, a carbon source and an iron salt catalyst are mixed and stirred uniformly with water to obtain mixed wet materials; the lithium salt solid waste powder is obtained after lithium salt minerals are treated by a nitric acid pressurization technology; the lithium salt solid waste powder comprises the following mass fractions of chemical compositions: SiO2 70-75%; Al2O3 20-25%; Impurity oxide 0-5%; The impurity oxide is a combination of one or more oxides of Fe2O3, K2O, CaO and MgO; The mixed wet materials are dried, then the dried mixture is calcined under the condition of an inert gas atmosphere, the calcination temperature is 600-900 DEG C, the calcination time is 3-9 hours, and then the mixture is cooled to room temperature to obtain the carbon nanomaterial in-situ modified lithium salt solid waste powder.

2. The method for producing a lithium salt solid waste powder in-situ modified with carbon nanomaterials according to claim 1, characterized by: The carbon source is one of anhydrous glucose, sucrose or corn straw, and the mass of the carbon source is 4-16% of the total mass of the carbon source and the lithium salt solid waste powder.

3. The method for preparing in-situ modified lithium salt solid waste powder using carbon nanomaterials according to claim 1, characterized in that: The iron salt catalyst is ferric nitrate or ferric chloride, and the mass of the iron salt catalyst is 20-80% of the mass of the carbon source.

4. The method for preparing in-situ modified lithium salt solid waste powder using carbon nanomaterials according to claim 1, characterized in that: During the mixing and stirring of the lithium salt solid waste powder, the carbon source and the iron salt catalyst with water, the stirring time is 6-24 hours.

5. A carbon nanomaterial in-situ modified lithium salt solid waste powder, characterized in that, The carbon nanomaterial in-situ modified lithium salt solid waste powder is prepared by the preparation method of the carbon nanomaterial in-situ modified lithium salt solid waste powder in any one of claims 1-4.

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