Pulse type pretreatment method for waste lithium battery pole core

Abstract

The application specifically discloses a pulse type pretreatment method for waste lithium battery pole cores, and the method comprises the following steps: performing pulse type pyrolysis defluorination replacement treatment on the waste lithium battery pole cores at a set pretreatment temperature Temp, wherein the total pretreatment time is t minutes, one pulse cycle time is T minutes, and the number of pulse cycles is T_num; wherein one pulse cycle comprises two steps, the first step is a defluorination reaction process of a cleavable hydrogen-containing gas, and the second step is an inert carrier gas replacement process. Through the defluorination reaction of the cleavable hydrogen-containing gas and the carrier gas replacement in multiple pulse cycles, the defluorination reaction is effectively promoted, and then the rapid reaction and removal of the gas phase fluorides are achieved. Moreover, the periodic pulse mode is used to strengthen the thermal decomposition of the binder in the electrode active material, and the adhesion between the electrode active material and the foil is reduced, and the peeling effect of the electrode active material is improved.

Description

Technical Field

[0001] This application belongs to the field of lithium battery recycling technology, and in particular relates to a pulse pretreatment method for waste lithium battery cores. Background Technology

[0002] Waste lithium-ion batteries contain toxic and harmful substances such as fluorine, organic solvents, and heavy metals, and must be recycled in a standardized manner. At the same time, waste lithium-ion batteries are also valuable "urban mines" containing metal elements such as lithium, copper, and aluminum, which are of great significance for realizing the closed-loop development of the lithium-ion battery industry chain.

[0003] In the process of recycling and reusing waste lithium batteries, one of the key steps at the front end is the pretreatment of the waste lithium battery cores. The purpose is to separate the electrode active materials from copper and aluminum foils to obtain battery black powder with lower copper and aluminum content.

[0004] Currently, the pretreatment methods for waste lithium battery cores generally involve coarse crushing, pyrolysis, fine crushing, and sorting (a combination of screening, air separation, magnetic separation, gravity separation, flotation, etc.) to achieve the following effects: First, reduce the bonding force between the electrode active material and the foil, so that the electrode active material can be peeled off from the foil surface; second, during the pyrolysis process, under certain temperature conditions, promote the complete or partial decomposition of organic solvents, non-fluorinated binders, fluorinated electrolytes, and fluorinated binders or additives contained in the lithium battery black powder. Part of the decomposition products are gaseous, and some of the harmful fluorinated substances originally contained in the lithium battery black powder are removed through the gas phase; third, during the sorting process, the active material is separated from the copper foil and aluminum as much as possible to obtain battery black powder with lower copper and aluminum content.

[0005] However, current methods for pre-treating spent lithium battery cells have the following problems and shortcomings:

[0006] First, the electrode active material remains tightly bonded to the foil, making peeling difficult. Current pretreatment methods, through pyrolysis, reduce the adhesion between the active material layer and the foil surface by breaking down the adhesive. Because the foil surface is roughened during the electrode fabrication process, the electrode active material forms a certain interlocking effect with the rough surface, preventing peeling. The pretreatment process can disrupt this interlocking effect to some extent. However, overall, current pretreatment methods still cannot achieve satisfactory peeling of the electrode active material from the foil.

[0007] Secondly, the fluorine content in the battery black powder obtained after pretreatment of waste lithium battery cores remains high. In the pretreatment process of waste lithium battery cores, pyrolysis is the key step in fluorine removal. Fluorine-containing substances decompose under temperature to generate hydrogen fluoride, which enters the gas phase and is removed. However, the actual pyrolysis defluorination process has a side effect: during removal, due to its high reactivity, the generated hydrogen fluoride also reacts chemically with metal elements in the electrode active material to form more stable metal fluorides. These metal fluorides remain in the battery black powder in solid form, resulting in a high fluorine content in the battery black powder.

[0008] Third, the battery black powder obtained after pretreatment of waste lithium battery cores has a high copper and aluminum content. Current pretreatment methods generally result in copper and aluminum content in the battery black powder exceeding 0.5%, which necessitates the removal of copper and aluminum impurities during subsequent battery black powder recycling, reducing economic efficiency.

[0009] Fourth, it poses challenges to the subsequent recycling of battery black powder, increasing costs. The high fluorine content in battery black powder severely affects the recovery of valuable elements in later processes. Furthermore, fluorine enters the gas, liquid, and solid phases in later processes, creating processing difficulties and increasing costs. The high copper and aluminum content in battery black powder reduces the amount of copper and aluminum recovered, resulting in value loss. Additionally, subsequent recycling processes for battery black powder require impurity removal of copper and aluminum, further increasing costs.

[0010] Therefore, there is an urgent need to develop a pretreatment technology for waste lithium battery cores that can promote good separation of electrode active materials from foil, has low fluorine content in battery black powder, and is low cost, so as to maximize the recycling value of waste lithium batteries. Summary of the Invention

[0011] This application is made in view of the above-mentioned technical problems. The purpose is to provide a pulse-type pretreatment method for waste lithium battery cores with high defluorination rate, high efficiency and low cost.

[0012] To address the aforementioned technical problems, this application provides a pulse-type pretreatment method for waste lithium battery cores, the method comprising:

[0013] At the set pretreatment temperature Temp, the waste lithium battery cores are subjected to pulsed thermal defluorination and replacement treatment. The total pretreatment time is t minutes, the pulse cycle time is T minutes, and the number of pulse cycles is T_num. The pulse cycle time T satisfies: 5 minutes ≤ T ≤ 60 minutes, and the number of pulse cycles T_num satisfies: 2 ≤ T_num ≤ 20.

[0014] One pulse cycle consists of two steps. The first step is the defluorination reaction of the crackable hydrogen-containing gas, with a reaction time of t1 minutes and a flow rate of V1 cubic meters per minute. The second step is the replacement process of the inert carrier gas, with a replacement time of t2 minutes and a flow rate of V2 cubic meters per minute. t1 and t2 satisfy the following conditions: 0.1≤t1 / t2≤10, and V1 and V2 satisfy the following condition: 1≤(V1*t1) / (V2*t2)≤10.

[0015] In some implementations, the total pretreatment time t satisfies: 30 minutes ≤ t ≤ 180 minutes, and the pretreatment temperature Temp satisfies: 500℃ ≤ Temp ≤ 650℃.

[0016] In some embodiments, the crackable hydrogen-containing gas refers to one or more of the following: hydrogen, hydrocarbon organic gases, water vapor, alcohol organic gases, acid organic gases, ester organic gases, and carbonate organic gases; the inert gas refers to one or more of the following: nitrogen, helium, and argon.

[0017] Compared with existing technologies, the pulse pretreatment method for waste lithium battery cores provided in this application has the following beneficial technical effects:

[0018] (1) This application uses multiple periodic pulse methods for pretreatment, which can effectively reduce the bonding force between the electrode active material and the foil, improve the peeling effect of the electrode active material, and make the electrode active material easy to separate from the surface of the lithium battery black powder core material. The copper and aluminum contents in the lithium battery black powder obtained after pretreatment are both less than 0.1%, realizing the efficient separation of copper and aluminum in the waste lithium battery core material. That is, in this application, the pulse method can enhance the thermal decomposition of the binder in the electrode active material. At the same time, the hydrogen-containing gas can be cracked to generate hydrogen atoms at a preset temperature to form a reducing atmosphere. The surface of the waste lithium battery core material is affected by the reducing atmosphere, and the bonding force between the electrode active material and the foil surface is greatly weakened.

[0019] (2) This application effectively promotes the efficient and deep removal of fluoride from lithium battery black powder by performing defluorination treatment with crackable hydrogen-containing gas and carrier gas replacement treatment in each pulse cycle, so that the fluoride content in the pretreated lithium battery black powder is less than 0.05%. In the process of removing fluoride from battery black powder by traditional pyrolysis method, due to the existence of the side synergistic effect, the competitive reaction of "fixed fluoride" occurs at the same time during the defluorination process. That is, the hydrogen fluoride gas generated in the defluorination process will also react chemically with the metal elements in the lithium battery black powder, thereby generating solid metal fluorides. The fluoride elements that should have been removed are instead fixed in the lithium battery black powder, making it difficult for the lithium battery black powder to remove fluoride cleanly and thoroughly. In this application, through the defluorination reaction process of crackable hydrogen-containing gas and inert carrier gas replacement treatment in multiple cycles, the defluorination reaction can be effectively promoted and the fixed fluoride reaction can be inhibited, thereby achieving the implementation effect of rapid reaction generation and rapid removal of gaseous fluorides, realizing the efficient and deep removal of fluoride from lithium battery black powder.

[0020] (3) This application can reduce the recycling cost of waste lithium battery cores. In this application, by concentrating and deeply removing fluorine at the front end, the cost of controlling and treating fluorine in the subsequent process can be greatly reduced, which is also conducive to the efficient recycling of other valuable elements; at the same time, this application achieves a high yield of copper and aluminum through efficient separation of copper and aluminum, that is, it reduces the content of copper and aluminum in lithium battery black powder, which reduces the cost of impurity removal on the one hand, and the direct recycling value of metallic copper and metallic aluminum is higher on the other hand.

[0021] In summary, the pulse pretreatment method for waste lithium battery cores provided in this application has the characteristics of high defluorination rate, high efficiency and low cost, and has a significant cost advantage compared with existing traditional processes. Attached Figure Description

[0022] To more clearly illustrate the specific embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the specific embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are some embodiments of the present invention. For those skilled in the art, other drawings can be obtained from these drawings without creative effort.

[0023] Figure 1 This is a process flow diagram of the pulse pretreatment method for waste lithium battery cores in this application. Detailed Implementation

[0024] The "range" disclosed in this application is defined by a lower limit and an upper limit. A given range is defined by selecting a lower limit and an upper limit, which define the boundaries of a particular range. Ranges defined in this way can include or exclude endpoints and can be arbitrarily combined; that is, any lower limit can be combined with any upper limit to form a range. For example, if ranges of 60-120 and 80-110 are listed for a specific parameter, it is expected that ranges of 60-110 and 80-120 are also included. Furthermore, if minimum range values ​​of 1 and 2 are listed, and if maximum range values ​​of 3, 4, and 5 are listed, then the following ranges are all expected: 1-3, 1-4, 1-5, 2-3, 2-4, and 2-5. In this application, unless otherwise stated, the numerical range "ab" represents a shortened representation of any combination of real numbers between a and b, where a and b are real numbers. For example, the numerical range "0-5" indicates that all real numbers between "0-5" have been listed in this article; "0-5" is simply a shortened representation of these numerical combinations. Furthermore, when a parameter is stated as an integer ≥2, it is equivalent to disclosing that the parameter is, for example, an integer such as 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, etc.

[0025] refer to Figure 1 As shown in the figure, this application provides a pulsed pretreatment method for waste lithium battery cores, the method comprising:

[0026] At the set pretreatment temperature Temp, the waste lithium battery cores are subjected to pulsed thermal defluorination and replacement treatment. The total pretreatment time is t minutes, the pulse cycle time is T minutes, and the number of pulse cycles is T_num. The pulse cycle time T satisfies: 5 minutes ≤ T ≤ 60 minutes, and the number of pulse cycles T_num satisfies: 2 ≤ T_num ≤ 20.

[0027] One pulse cycle consists of two steps. The first step is the defluorination reaction of the crackable hydrogen-containing gas, with a reaction time of t1 minutes and a flow rate of V1 cubic meters per minute. The second step is the replacement process of the inert carrier gas, with a replacement time of t2 minutes and a flow rate of V2 cubic meters per minute. t1 and t2 satisfy the following conditions: 0.1≤t1 / t2≤10, and V1 and V2 satisfy the following condition: 1≤(V1*t1) / (V2*t2)≤10.

[0028] The crackable hydrogen-containing gas refers to one or more of the following: hydrogen, hydrocarbon organic gases, water vapor, alcohol organic gases, acid organic gases, ester organic gases, and carbonate organic gases; the inert gas refers to one or more of the following: nitrogen, helium, and argon; the total pretreatment time t satisfies: 30 minutes ≤ t ≤ 180 minutes, and the pretreatment temperature Temp satisfies: 500℃ ≤ Temp ≤ 650℃.

[0029] In this embodiment, at a preset temperature (Temp), the introduced crackable hydrogen-containing gas is catalytically cracked, releasing hydrogen atoms. Based on the released hydrogen atoms, a defluorination chemical reaction is carried out with fluorine atoms or metal fluorides generated from the cracking of fluorine-containing substances in the waste lithium battery electrode core raw materials, thereby achieving the removal of fluorine from the waste lithium battery electrode core raw materials. Wherein:

[0030] The catalytic cracking chemical reaction formula for cracking hydrogen-containing gases is as follows:

[0031] RH(g)=H·(g)+R·(g) (1)

[0032] The chemical reaction formula for the defluorination reaction is as follows:

[0033] H·(g) + F·(g) = HF(g) (2)

[0034] H·(g)+OH·(g)+LiF=HF(g)+LiOH (3).

[0035] In this embodiment, based on multiple periodic pulses, the thermal decomposition of the binder in the electrode active material is enhanced. The hydrogen atoms generated by the catalytic cracking of the introduced crackable hydrogen gas at a preset temperature form a reducing atmosphere. This atmosphere affects the surface of the waste lithium battery core material, significantly weakening the bonding force between the electrode active material and the foil surface. This reduces the bonding force between the electrode active material and the surface of the waste lithium battery core material, improving the peeling effect of the electrode active material. This makes it easier for the electrode active material to separate from the surface of the lithium battery black powder core material. The copper and aluminum content in the lithium battery black powder obtained after pretreatment can reach below 0.1%, achieving efficient separation of copper and aluminum from the waste lithium battery core material. At the same time, the multiple cycles of crackable hydrogen gas defluorination reaction and inert carrier gas replacement treatment effectively promote the defluorination reaction and inhibit the solid fluoride reaction, thereby achieving the effect of rapid reaction generation and rapid removal of gaseous fluorides, realizing efficient and deep removal of fluoride from the lithium battery black powder. Therefore, the pulse pretreatment method for waste lithium battery cores provided in this application has the characteristics of high defluorination rate, high efficiency and low cost, and has a significant cost advantage compared with existing traditional processes.

[0036] Because the hydrogen fluoride gas generated in the defluorination reaction has high chemical reactivity, it readily reacts with metal elements in the electrode active material to form metal fluorides, i.e., a "fixed fluoride" side reaction occurs. The chemical reaction formula for the fixed fluoride reaction is as follows:

[0037]

[0038] In equations (4) and (5), Me represents metallic elements such as Fe, Cu, Al, Ni, Co, and Mn. In order to reduce the occurrence of the "fixed fluorine" side reaction in equations (4) and (5), in this embodiment, the defluorination reaction is carried out first within one pulse cycle, and then the inert carrier gas is used for replacement. Based on the fact that the inert carrier gas can quickly remove the HF gas generated in the defluorination process of the crackable hydrogen-containing gas, the occurrence of the side reaction is suppressed by reducing the reactant concentration of the "fixed fluorine" reaction. In order to achieve a deep defluorination effect, this embodiment adopts a multi-cycle enhanced pulse mode to remove the fluorine content in the waste lithium battery electrode core raw materials step by step. At the same time, the organic solvent is fully removed and the binder is fully decomposed.

[0039] In this embodiment, each pulse cycle can be any value between 5 and 60 minutes, for example, 5 minutes, 10 minutes, 15 minutes, 20 minutes, 25 minutes, 30 minutes, 35 minutes, 40 minutes, 45 minutes, 50 minutes, 55 minutes, 60 minutes, etc., and the number of pulse cycles can be any value between 2 and 20, for example, 2, 5, 8, 11, 14, 17, 20, etc. In practical applications, the time of each pulse cycle needs to be set according to the actual situation. If the time is set too short, the short time is beneficial for suppressing the solid fluoride reaction, but the reaction time between the crackable hydrogen-containing gas and the fluorine in the waste lithium battery electrode core material is insufficient, and the defluorination effect may be poor. If the time is set too long, the reaction time between the crackable hydrogen-containing gas and the fluorine in the waste lithium battery electrode core material is sufficient, but it is not conducive to suppressing the solid fluoride reaction, and the defluorination effect is also poor. At the same time, if the number of pulse cycles is too large, the time consumption is too long, which is not conducive to improving work efficiency; if the number of pulse cycles is too small, it is not conducive to the defluorination effect. Therefore, the duration and number of pulse cycles should be adjusted based on the actual removal effect.

[0040] In some embodiments, the process also includes sorting the waste lithium battery core raw materials after periodic pulse pretreatment to obtain metallic copper, metallic aluminum, and lithium battery black powder.

[0041] In the above embodiments, by sorting the waste lithium battery core raw materials after periodic pulse pretreatment, lithium battery black powder, metallic copper and metallic aluminum are finally obtained, realizing the efficient separation of fluorine, copper, aluminum and waste lithium battery core raw materials, and providing a guarantee for the further recycling of lithium battery black powder.

[0042] The following embodiments describe the disclosure of this application in more detail. These embodiments are merely illustrative, as various modifications and variations within the scope of the disclosure of this application will be apparent to those skilled in the art. Unless otherwise stated, all reagents and raw materials used in the embodiments are commercially available or synthesized by conventional methods, and the instruments and equipment used in the embodiments are also commercially available.

[0043] Example 1

[0044] 1) Dissect the waste lithium batteries, remove the electrode cores, and send 1000 kg of electrode cores into a pretreatment reaction device with a preset temperature of Temp = 500℃ for the first pulse cycle pretreatment. First, water vapor with a flow rate of V1 = 9.6 m3 / min is introduced into the pretreatment reaction device. The introduced water vapor fully contacts the waste lithium battery electrode cores and carries out a defluorination reaction for a time of t1 = 20 minutes. Then, the water vapor is stopped, and nitrogen gas with a flow rate of V2 = 8 m3 / min is introduced as the carrier gas for replacement. The nitrogen replacement time is t2 = 10 minutes. The time of the first pulse cycle is T = t1 + t2 = 30 minutes, which satisfies 5 minutes ≤ T ≤ 60 minutes. The second and third pulse cycle pretreatments are carried out in sequence using the same steps, and the waste lithium battery electrode cores after pulse pretreatment are cooled to room temperature.

[0045] 2) The cooled waste lithium battery cores are sorted into metallic copper, metallic aluminum, and battery black powder, and finally lithium battery black powder, metallic copper, and metallic aluminum are obtained.

[0046] In this embodiment, the number of periodic pulses Tnum = 3, satisfying 2 ≤ Tnum ≤ 20; the defluorination reaction time and the inert carrier gas replacement time t1 / t2 = 2, satisfying 0.1 ≤ t1 / t2 ≤ 10; the relationship between the flow rate of the crackable hydrogen-containing gas, the flow rate of the inert carrier gas, the defluorination reaction time, and the carrier gas replacement time is: (V1*t1) / (V2*t2) = 2.4, satisfying 1 ≤ (V1*t1) / (V2*t2) ≤ 10; the total pretreatment time t = 90 minutes, satisfying 30 minutes ≤ t ≤ 180 minutes.

[0047] Example 2

[0048] 1) Dissect the waste lithium batteries, remove the electrode cores, and send 1000 kg of electrode cores into a pretreatment reaction device with a preset temperature of Temp = 600℃ for the first pulse cycle pretreatment. First, natural gas with a flow rate of V1 = 2.2 m3 / min is introduced into the pretreatment reaction device. The introduced water vapor fully contacts the waste lithium battery electrode cores and carries out a defluorination reaction for a time of t1 = 10 minutes. Then, the natural gas supply is stopped, and nitrogen with a flow rate of V2 = 4 m3 / min is introduced as the carrier gas for replacement. The nitrogen replacement time is t2 = 5 minutes. The time of the first pulse cycle is T = t1 + t2 = 15 minutes, which satisfies 5 minutes ≤ T ≤ 60 minutes. The same steps are repeated for the second, third, and fourth pulse cycle pretreatments, and the waste lithium battery electrode cores after pulse pretreatment are cooled to room temperature.

[0049] 2) The cooled waste lithium battery cores are sorted into metallic copper, metallic aluminum, and battery black powder, and finally lithium battery black powder, metallic copper, and metallic aluminum are obtained.

[0050] In this embodiment, the number of periodic pulses Tnum = 4, satisfying 2 ≤ Tnum ≤ 20; the defluorination reaction time and the inert carrier gas replacement time t1 / t2 = 2, satisfying 0.1 ≤ t1 / t2 ≤ 10; the relationship between the flow rate of the crackable hydrogen-containing gas, the flow rate of the inert carrier gas, the defluorination reaction time, and the carrier gas replacement time is: (V1*t1) / (V2*t2) = 1.1, satisfying 1 ≤ (V1*t1) / (V2*t2) ≤ 10; the total pretreatment time t = 60 minutes, satisfying 30 minutes ≤ t ≤ 180 minutes.

[0051] Example 3

[0052] 1) Dissect the waste lithium batteries, remove the electrode cores, and send 1000 kg of electrode cores into a pretreatment reaction device with a preset temperature of Temp = 650℃ for the first pulse cycle pretreatment. First, a mixed gas with a flow rate of V1 = 38.5 m3 / min is introduced into the pretreatment reaction device. The mixed gas includes water vapor and natural gas with a volume ratio of 95:5. The introduced mixed gas fully contacts the waste lithium battery electrode cores and carries out a defluorination reaction for a time of t1 = 10 minutes. Then, the mixed gas is stopped, and nitrogen with a flow rate of V2 = 9 m3 / min is introduced as the carrier gas for replacement. The nitrogen replacement time is t2 = 5 minutes. The time of the first pulse cycle is T = t1 + t2 = 15 minutes, which satisfies 5 minutes ≤ T ≤ 60 minutes. The same steps are repeated for the second, third, fourth, and fifth pulse cycle pretreatments. After the pulse pretreatment, the waste lithium battery electrode cores are cooled to room temperature.

[0053] 2) The cooled waste lithium battery cores are sorted into metallic copper, metallic aluminum, and battery black powder, and finally lithium battery black powder, metallic copper, and metallic aluminum are obtained.

[0054] In this embodiment, the number of periodic pulses Tnum = 5, satisfying 2 ≤ Tnum ≤ 20; the defluorination reaction time and the inert carrier gas replacement time t1 / t2 = 2, satisfying 0.1 ≤ t1 / t2 ≤ 10; the relationship between the flow rate of the crackable hydrogen-containing gas, the flow rate of the inert carrier gas, the defluorination reaction time, and the carrier gas replacement time is: (V1*t1) / (V2*t2) = 8.6, satisfying 1 ≤ (V1*t1) / (V2*t2) ≤ 10; the total pretreatment time t = 75 minutes, satisfying 30 minutes ≤ t ≤ 180 minutes.

[0055] The lithium battery black powder obtained in Examples 1-3 was tested for fluorine, aluminum and copper content, and the test results are shown in Table 1.

[0056] Table 1. Detection results of fluorine, aluminum, and copper content in lithium battery black powder from Examples 1-3.

[0057] F(％) Al(％) Cu (%) Example 1 0.036 0.073 0.082 Example 2 0.043 0.076 0.085 Example 3 0.027 0.056 0.064

[0058] As can be seen from Table 1, the fluorine, aluminum, and copper contents in the lithium battery black powder obtained in Examples 1, 2, and 3 are all below 0.1%, indicating that Examples 1-3 have all achieved effective separation and removal of fluorine, copper, and aluminum from waste lithium battery core raw materials. Therefore, the pulse pretreatment method provided in this application can effectively remove fluorine, copper, and aluminum from lithium battery black powder, which reduces the cost of controlling and treating fluorine, copper, and aluminum in subsequent processes. It has the characteristics of high efficiency and low cost, and provides favorable conditions for the subsequent recycling and treatment of lithium battery black powder.

[0059] The pulse-type pretreatment method for waste lithium battery cores provided in this application has been described in detail above. Specific examples have been used to illustrate the principles and implementation methods of this application. The descriptions of the embodiments above are only for the purpose of helping to understand the core ideas of this application. It should be noted that those skilled in the art can make several improvements and modifications to this application without departing from the principles of this application, and these improvements and modifications also fall within the protection scope of the claims of this application.

Claims

1. A pulse-type pretreatment method for waste lithium battery cores, characterized in that, The method includes: At the set pretreatment temperature Temp, the waste lithium battery cores are subjected to pulsed thermal defluorination and replacement treatment. The total pretreatment time is t minutes, the pulse cycle time is T minutes, and the number of pulse cycles is T_num. The pulse cycle time T satisfies: 5 minutes ≤ T ≤ 60 minutes, and the number of pulse cycles T_num satisfies: 2 ≤ T_num ≤ 20. One pulse cycle consists of two steps. The first step is the defluorination reaction of the crackable hydrogen-containing gas, with a reaction time of t1 minutes and a flow rate of V1 cubic meters per minute. The second step is the replacement process of the inert carrier gas, with a replacement time of t2 minutes and a flow rate of V2 cubic meters per minute. t1 and t2 satisfy the following conditions: 0.1≤t1 / t2≤10, and V1 and V2 satisfy the following condition: 1≤(V1*t1) / (V2*t2)≤10.

2. The pulse pretreatment method for waste lithium battery cores as described in claim 1, characterized in that, The total pretreatment time t satisfies: 30 minutes ≤ t ≤ 180 minutes, and the pretreatment temperature Temp satisfies: 500℃ ≤ Temp ≤ 650℃.

3. The pulse-type pretreatment method for waste lithium battery cores as described in claim 1 or 2, characterized in that, The crackable hydrogen-containing gas refers to one or more of the following: hydrogen, hydrocarbon organic gases, water vapor, alcohol organic gases, acid organic gases, and ester organic gases; the inert carrier gas refers to one or more of the following: nitrogen, helium, and argon.

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