CN112542581A - Method for preparing pre-lithiation agent in electrochemical process - Google Patents
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Abstract
The invention belongs to the technical field of lithium ion batteries, and discloses a method for preparing a pre-lithiation agent in an electrochemical process, which specifically comprises the steps of selecting an active material, preparing the active material into an electrode serving as a working electrode, taking metal lithium as a counter electrode, and adding an electrolyte to assemble a battery; then, discharging the battery to lithiate the working electrode; and finally, disassembling the battery, separating and collecting substances obtained after the active material is converted, and then cleaning and drying to obtain the pre-lithiation agent material. According to the invention, the whole process of the preparation method is improved, based on an electrochemical principle, the active material of a specific compound type is utilized, and lithiation is realized through discharging to obtain the pre-lithiation agent material.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a method for preparing a pre-lithiation agent in an electrochemical process, which can realize in-situ preparation of the pre-lithiation agent.
Background
A lithium ion battery is a commonly used high-performance secondary battery. The active lithium source in current lithium ion batteries is provided by the positive electrode. When the battery is first charged, a Solid Electrolyte Interface (SEI) is formed on the surface of the negative electrode, consuming a portion of active lithium, resulting in a decrease in the capacity and energy density of the battery. After the graphite cathode of the lithium ion battery is replaced by the silicon-based cathode, more lithium is consumed in the process of forming the silicon-based cathode SEI, the initial coulombic efficiency of the battery is lower, and the capacity and the energy density of the battery are limited to a certain extent.
The method for compensating lithium of the battery by adopting the pre-lithiation agent is an effective method for overcoming the lithium loss in the first charging and discharging process and improving the energy density of the battery. However, the relevant pre-lithiation agent materials have complex synthesis process, poor safety in the synthesis process, harsh preparation environmental conditions and large difficulty in large-scale operation, and the main reasons are that the existing pre-lithiation additive generally reacts a material to be lithiated with a metal lithium foil or metal lithium powder under the condition of heating at high temperature, the final product of the reaction is in a powder shape, the metal lithium is an active metal, the safety and controllability in the reaction process are poor, and the energy consumption is relatively high due to high-temperature reaction.
Disclosure of Invention
In view of the above defects or improvement needs of the prior art, an object of the present invention is to provide a method for preparing a pre-lithiation agent in an electrochemical process, wherein the whole process of the preparation method is improved, and based on an electrochemical principle, an active material of a specific compound type is used to perform lithiation through discharge to obtain a pre-lithiation agent material.
To achieve the above object, according to one aspect of the present invention, there is provided a method for preparing a prelithiation agent by an electrochemical process, comprising the steps of:
(1) taking a lithium-containing oxide positive electrode material, or a metal oxide, or a metal fluoride, or a metal oxyfluoride, or a simple substance of an element A capable of forming an alloy or a compound or a solid solution with lithium, or an oxide of the element A, or a fluoride of the element A, or an oxyfluoride of the element A as an active material, preparing the active material into an electrode serving as a working electrode, taking metal lithium as a counter electrode, and adding an electrolyte to assemble a battery;
(2) discharging the battery obtained in the step (1) to lithiate the working electrode in the battery, so that an active material in the working electrode is converted into a mixture of a simple metal substance and LiF, or the simple metal substance and Li2O mixture, or metal element, LiF and Li2A mixture of O, or an alloy or a compound or a solid solution of said element A and a lithium element, or Li2A mixture of O and the alloy or compound or solid solution, or a mixture of LiF and the alloy or compound or solid solution, or LiF and Li2Mixtures of O with the alloys or compounds or solid solutions;
(3) and (3) disassembling the battery subjected to discharge treatment in the step (2), separating and collecting substances obtained after active material conversion, and then cleaning and drying to obtain the pre-lithiation agent material.
According to another aspect of the present invention, there is provided a method of preparing a prelithiation agent by an electrochemical process, comprising the steps of:
(1) the active material is prepared into an electrode as a working electrode by taking a lithium-containing oxide positive electrode material, a metal oxide, a metal fluoride, a metal oxyfluoride, or a simple substance of an element A capable of forming an alloy or a compound or a solid solution with lithium, or an oxide of the element A, a fluoride of the element A or an oxyfluoride of the element A as the active material,
(2) wetting the working electrode obtained in the step (1) by using an electrolyte, and then short-circuiting the wetted working electrode with a lithium metal cathode to lithiate the working electrode, so that an active material in the working electrode is converted into a mixture of a metal simple substance and LiF, or the metal simple substance and Li2O mixture, or metal element, LiF and Li2A mixture of O, or an alloy or a compound or a solid solution of said element A and a lithium element, or Li2A mixture of O and the alloy or compound or solid solution, or a mixture of LiF and the alloy or compound or solid solution, or LiF and Li2And a mixture of O with the alloy or compound or solid solution to obtain a prelithiating agent material.
As a further preferred aspect of the present invention, in the step (1), the metal element contained in the lithium-containing oxide cathode material in addition to Li element, and the metal element contained in the metal oxide, the metal fluoride, and the metal oxyfluoride are each selected from one or more of cobalt (Co), iron (Fe), manganese (Mn), nickel (Ni), titanium (Ti), zirconium (Zr), chromium (Cr), vanadium (V), molybdenum (Mo), copper (Cu), zinc (Zn), aluminum (Al), lead (Pb), magnesium (Mg), and ruthenium (Ru).
As a further preferred aspect of the present invention, in the step (1), the element a capable of forming an alloy or a compound or a solid solution with lithium is selected from one or more of silicon (Si), germanium (Ge), tin (Sn), phosphorus (P), aluminum (Al), sulfur (S), selenium (Se), magnesium (Mg), and zinc (Zn).
As a further preferred aspect of the present invention, in the step (1), the mass percentage of the active material in the working electrode is 5% to 99.5%; the working electrode also comprises a conductive agent and a binder, wherein the sum of the mass of the conductive agent and the mass of the binder accounts for 0.5-95% of the total mass of the working electrode.
In the present invention, it is preferable that in the step (2), the discharge cutoff voltage range in the discharge treatment is 0 to 2V.
As a further preferred aspect of the present invention, the step (3) is specifically:
disassembling the battery subjected to the discharge treatment in the step (2), removing the electrolyte on the surface of the working electrode, mechanically separating the working electrode from the current collector, and mechanically crushing the separated working electrode into a powder material, thereby obtaining a crude product containing the substance obtained after the active material is converted.
As a further preferred aspect of the present invention, the step (3) further comprises: and (3) separating the crude product to separate out the conductive agent and the binder, so as to obtain a refined product containing substances obtained after the active material is converted.
By the above technical solution conceived by the present invention, compared to the prior art, the positive active material is utilized, i.e. with lithium-containing oxide positive electrode material (Li)xMyOzWherein x, y and z are all non-zero integers and satisfy x +3y ═ 2z), or a metal oxide (M)xOy) Or metal fluoride (M)xFy) Or metal oxyfluoride salt (M)xOyFz) Or a simple substance (A) of an element A capable of forming an alloy or a compound or a solid solution with lithium or an oxide (A) of the element AxOy) Or a fluoride of the element A (A)xFy) Or a oxyfluoride salt of the element A (A)xOyFz) An active material (wherein x and y in the chemical general formula of oxides, fluorides, oxyfluorides and alloying substances have no specific proportional relationship as long as the properties of the elements of the material itself can be satisfied), an electrode is prepared as a working electrode, a battery is assembled by an electrochemical method, for example, with a metallic lithium negative electrode, an electrolyte and the like (in this case, the working electrode is used as a positive electrode plate), the active material is lithiated by a discharge treatment to form a pre-lithiation agent material target product, the battery is disassembled, the active material in the working electrode is separated from a current collector, and necessary post-treatments such as washing, drying and collection are carried out, so that the active material with the general formula of M/Li is obtained2O (i.e. elemental metals M and Li)2O mixtures, similar below), M/LiF @Li2O、LixAy、LixAy/Li2O、LixAyLiF or LixAy/LiF/Li2The pre-lithiation agent material target product of O can be used as a pre-lithiation additive. Of course, besides the process of electrochemical lithiation by assembling the lithium battery, the electrochemical reaction device (i.e. the device for preparing the material by the electrochemical reaction) adopted by the invention can adopt other reaction devices with controllable electrochemical lithiation process instead of the conventional battery, so that the conventional battery structure is not required to be assembled and disassembled for packaging and the like, and the large-scale preparation of the pre-lithiation material is realized.
The pre-lithiation agents obtained by the preparation method are M/LiF and M/Li2O、M/LiF/Li2O (M may be one or more transition metals or mainly transition metals and include other elements capable of combining with or alloying with or dissolving in lithium, such as Co, Fe, Mn, Ni, Ti, Zr, Cr, V, Mo, Cu, Al, Pb, Mg, Ru, Zn, etc.) or LixAyOr LixAy/Li2O or LixAyLiF or LixAy/LiF/Li2O (A can be one or more element materials capable of forming an alloy or a compound or a solid solution with metallic lithium, such as Si, Ge, Sn, P, Al, S, Se, Zn, Mg and the like) can be used as a prelithiation additive to perform lithium compensation on the lithium battery.
Compared with the existing common chemical synthesis method for preparing the pre-lithiation agent, the method has the advantages that: (1) compared with the prior art that the pre-lithiation agent is prepared by carrying out chemical reaction on metal oxide, metal fluoride, alloy and the like and metal lithium under a heating condition, the preparation method disclosed by the invention utilizes an electrochemical reaction process, the reaction process is controllable, the lithium content of the prepared material is controllable, and the safety of the preparation method has advantages; (2) the scale of the electrode/battery can be regulated to regulate the active substance and the yield, and the controllable batch production of the material can be realized; (3) the preparation method of the pre-lithiation agent is matched with the existing battery technology, can be produced under the existing technological conditions of enterprises, and is beneficial to large-scale commercial application.
The invention uses electrochemical method to prepare pre-lithiation agent, uses the lithiation process of material under the condition of discharge voltage, and can judge that lithiation is produced or not when the material reaches preset specified voltage so as to define that the material is completely lithiated or not, and the completely lithiated material has high specific capacity, for example, alloy type Li obtained after Al is lithiated9Al4The actual capacity of the composite material can reach 1100 mAh/g.
The invention also can ensure that the material on the working electrode is completely lithiated (or is mostly lithiated) by further preferably regulating and controlling the voltage parameter condition of the electrochemical lithiation process (namely, discharge treatment) and controlling the cut-off voltage range to be 0-2V. When the discharging process of the battery reaches a preset target voltage, the battery can be disassembled subsequently, the active substances on the pole piece and the current collector are stripped, and then the electrode containing the active substances after stripping is subjected to necessary cleaning, drying, collecting and other treatments, so that the active pre-lithiation agent material can be obtained. The voltage range selected by the invention is 0-2V, and the materials which can be commonly applied at present can be completely lithiated or partially lithiated in the voltage range, such as LiCoO2The lithiation voltage is around 1.2V, while the lithiation voltage of Al is around 0.3V. According to the preparation method of the present invention, voltage can be used as a characteristic value of completion of lithiation, and a material can react with lithium intercalation and lithium deintercalation at a specific voltage, so that lithiation can be realized by discharging to the cut-off voltage by setting the cut-off voltage (the cut-off voltage can be usually set to be lower than the voltage at which lithiation occurs, and the cut-off voltage is different depending on the lithiation voltage of different materials).
Compared with other methods for preparing the pre-lithiation agent, the electrochemical method is adopted for lithiation to replace a chemical method, lithiation and delithiation can occur in the battery in the charging and discharging processes, the lithiation and delithiation are regarded as an electrochemical phenomenon in the existing research, and the electrochemical method is not researched and developed as a material synthesis method.
In conclusion, compared with the prior art, the invention has the following beneficial effects:
1. the preparation method disclosed by the invention is used for preparing the pre-lithiation agent through the electrochemical process of the battery, the preparation process of the material is relatively smooth, a large amount of heat is not generated, and the safety and controllability of the material preparation are effectively improved. The method for synthesizing the pre-lithiation agent M/Li by assembling the battery to carry out electrochemical lithiation2O、M/LiF、M/LiF/Li2O、LixAy、LixAy/Li2O、LixAyLiF and LixAy/LiF/Li2Compared with the existing method for preparing the pre-lithiation agent through high-temperature solid-phase reaction, the method has the advantages of mild process and highly controllable lithiation degree.
2. The yield of the material can be controlled by controlling the loading capacity and the size of the working electrode pole piece, the yield is improved by adopting a high-loading battery, and the large-scale production can be realized. The mass (i.e., loading) of the active material carried by the battery plate per unit area can be adjusted in a wide range according to the process, production requirements and manufacturing scale, for example, the electrode mass loading of the working electrode in the present invention can be 0.5-200mg/cm2And even larger.
3. The production method is realized by disassembling and assembling the battery, the production can be finished by adopting the existing battery process, and the matching property with industrial production is good.
4. The production method can also avoid the assembly and disassembly of the traditional battery device, thereby effectively reducing the cost of the method.
Drawings
FIG. 1 is a schematic view of a production process of the present invention.
Fig. 2 is a schematic diagram of a battery used in the present invention, and the main structure is a current collector, a working electrode, an electrolyte, a separator, an electrolyte and a lithium metal electrode in the order from left to right as shown in the figure.
Fig. 3 is a schematic diagram of a reaction apparatus with controllable electrochemical lithiation process according to the present invention.
FIG. 4 is Fe2O3、FeOF、FeF3And (3) carrying out discharge curves in the discharge lithiation process of the three active materials.
Fig. 5 is a charging curve of three materials after lithiation.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
Example one
Mixing 800mg of lithium cobaltate, 100mg of conductive agent (Super P) and 100mg of PVDF (5 wt% PVDF/NMP solution), homogenizing, coating, vacuum drying at 60 ℃ to obtain a working electrode, assembling the working electrode and metallic lithium into a battery, discharging the battery until the voltage of the battery is 0V, disassembling an electrode plate, cleaning and drying to obtain Co/Li2O a pre-lithiating agent. Obtained Co/Li2The O pre-lithiation agent can be used as an additive and is added into the positive electrode of a conventional battery in a small amount by a slurry mixing and pressing method to play a role of pre-lithiation.
Example two
Taking 800mg of Li2Ni0.8Co0.1Mn0.1O2Mixing 100mg of conductive agent (Super P) and 100mg of PVDF (5 wt% PVDF/NMP solution), homogenizing, coating, vacuum drying at 60 ℃ to obtain a working electrode, assembling the working electrode and metallic lithium into a battery, discharging the battery to 0V, disassembling an electrode plate, cleaning and drying to obtain Ni/Co/Mn/Li2O a pre-lithiating agent. The obtained Ni/Co/Mn/Li2The O pre-lithiation agent can be used as an additive and is added into the positive electrode of a conventional battery in a small amount by a slurry mixing and pressing method to play a role of pre-lithiation.
EXAMPLE III
Mixing 700mg FeOOF, 200mg conductive agent (Super P) and 100mg PVDF (5 wt% PVDF/NMP solution), homogenizing, coating, vacuum drying at 60 deg.C to obtain working electrode, assembling with lithium metal to obtain battery, discharging the battery, and discharging the battery to voltageAt 0V, disassembling the electrode plate, cleaning and drying to obtain Fe/LiF/Li2O a pre-lithiating agent. The Fe/LiF/Li obtained2The O pre-lithiation agent can be used as an additive and is added into the positive electrode of a conventional battery in a small amount by a slurry mixing and pressing method to play a role of pre-lithiation.
FIG. 1 is a flow chart of an experiment according to the preparation method described in the present invention, and the flow of steps occurring in the experimental process is shown in the figure.
Fig. 2 is a schematic diagram of a battery used in the invention, and the battery internally comprises a working electrode, a lithium negative electrode, a diaphragm and an electrolyte, wherein the working electrode material is a raw material for synthesizing a pre-lithiation agent, and the battery is a soft package battery or other types.
The electrochemical reaction device (namely, the device for preparing the material by the electrochemical reaction) adopted by the invention can adopt other reaction devices with controllable electrochemical lithiation processes instead of a conventional battery form, so that the condition that the package and the like need to be assembled and disassembled by using a conventional battery structure is avoided, and the large-scale preparation of the pre-lithiation material is carried out. Fig. 3 is a schematic diagram of a non-conventional battery device used in the present invention, in which the electrochemical lithiation process can be controlled by current/voltage, with a discharge cut-off voltage range of 0-2V. The design avoids the need of assembling and disassembling packages and the like by using a conventional battery structure, and is beneficial to large-scale preparation of the pre-lithiation material.
Fig. 4 is a first discharge curve of three materials, the active material in the prepared pole piece: carbon black: PVDF 7:2:1, can be discharged to a set cut-off voltage to lithiate the three and other materials to synthesize a prelithiating agent material.
Fig. 5 is the first charge curve (matching fig. 4) after lithiation of the three materials. As is clear from fig. 4 and 5, by controlling the Li insertion amount, the degree of reaction, i.e., the degree of lithiation, it can be seen that the lithiated material can release a high specific lithium ion capacity and can be used as a prelithiation agent. The invention is based on the charge and discharge principle of the battery, and takes the material needing lithiation as the anode and the metal lithium as the cathode, when discharging, the cathode loses electrons, the lithium is converted into lithium ions, and the lithium ions are separated to move to the anode and are embedded into the anode, thereby realizing the process of electrochemical pre-lithiation; the lithiated material is added as an additive to the battery during subsequent charging, and in contrast to this, will extract the intercalated lithium, thereby compensating for the loss of lithium. Thus, the capacity of the discharge curve as shown in fig. 4 represents the amount of intercalated lithium, while the capacity of the charge curve as shown in fig. 5 represents how much intercalated lithium can be extracted.
As shown in fig. 1, the process of separating and collecting the pre-lithiation agent product after the discharge reaction can be as follows: disassembling the battery, separating active substances from a current collector, performing necessary treatments such as cleaning, drying, collecting and the like, removing electrolyte on the surface of an electrode, mechanically separating the electrode and the current collector, and mechanically crushing the electrode into powder materials; whether to separate out electrode additives such as conductive agents and the like can be selected according to the conditions, whether to carry out solvent cleaning on active material powder can be selected according to the conditions, and the active material powder is collected after drying.
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (8)
1. A method of preparing a prelithiation agent in an electrochemical process, comprising the steps of:
(1) taking a lithium-containing oxide positive electrode material, or a metal oxide, or a metal fluoride, or a metal oxyfluoride, or a simple substance of an element A capable of forming an alloy or a compound or a solid solution with lithium, or an oxide of the element A, or a fluoride of the element A, or an oxyfluoride of the element A as an active material, preparing the active material into an electrode serving as a working electrode, taking metal lithium as a counter electrode, and adding an electrolyte to assemble a battery;
(2) discharging the battery obtained in the step (1) to lithiate the working electrode in the battery, so that an active material in the working electrode is converted into a mixture of a simple metal substance and LiF, or the simple metal substance and Li2Of OMixtures or elemental metals with LiF and Li2A mixture of O, or an alloy or a compound or a solid solution of said element A and a lithium element, or Li2A mixture of O and the alloy or compound or solid solution, or a mixture of LiF and the alloy or compound or solid solution, or LiF and Li2Mixtures of O with the alloys or compounds or solid solutions;
(3) and (3) disassembling the battery subjected to discharge treatment in the step (2), separating and collecting substances obtained after active material conversion, and then cleaning and drying to obtain the pre-lithiation agent material.
2. A method of preparing a prelithiation agent in an electrochemical process, comprising the steps of:
(1) taking a lithium-containing oxide positive electrode material, or a metal oxide, or a metal fluoride, or a metal oxyfluoride, or a simple substance of an element A capable of forming an alloy or a compound or a solid solution with lithium, or an oxide of the element A, or a fluoride of the element A, or an oxyfluoride of the element A as an active material, and preparing the active material into an electrode as a working electrode;
(2) wetting the working electrode obtained in the step (1) by using an electrolyte, and then short-circuiting the wetted working electrode with a lithium metal cathode to lithiate the working electrode, so that an active material in the working electrode is converted into a mixture of a metal simple substance and LiF, or the metal simple substance and Li2O mixture, or metal element, LiF and Li2A mixture of O, or an alloy or a compound or a solid solution of said element A and a lithium element, or Li2A mixture of O and the alloy or compound or solid solution, or a mixture of LiF and the alloy or compound or solid solution, or LiF and Li2And a mixture of O with the alloy or compound or solid solution to obtain a prelithiating agent material.
3. The method for preparing a prelithiating agent according to the electrochemical process of claim 1 or 2, wherein in the step (1), the metal elements contained in the lithium-containing oxide cathode material, excluding the Li element, and the metal elements contained in the metal oxide, the metal fluoride, and the metal oxyfluoride, are selected from one or more of cobalt (Co), iron (Fe), manganese (Mn), nickel (Ni), titanium (Ti), zirconium (Zr), chromium (Cr), vanadium (V), molybdenum (Mo), copper (Cu), zinc (Zn), aluminum (Al), lead (Pb), magnesium (Mg), and ruthenium (Ru).
4. The method for preparing a pre-lithiating agent by an electrochemical process according to claim 1 or 2, wherein in the step (1), the element a capable of forming an alloy or a compound or a solid solution with lithium is selected from one or more of silicon (Si), germanium (Ge), tin (Sn), phosphorus (P), aluminum (Al), sulfur (S), selenium (Se), magnesium (Mg), and zinc (Zn).
5. The method for preparing a pre-lithiation agent through an electrochemical process according to claim 1 or 2, wherein in the step (1), the mass percentage of the active material in the working electrode is 5% to 99.5%; the working electrode also comprises a conductive agent and a binder, and preferably, the sum of the mass of the conductive agent and the mass of the binder accounts for 0.5-95% of the total mass of the working electrode.
6. The method for preparing a prelithiation agent according to the electrochemical process of claim 1, wherein in the step (2), the cut-off voltage of discharge in the discharge treatment is in the range of 0 to 2V.
7. The method for preparing a pre-lithiation agent by an electrochemical process according to claim 1, wherein the step (3) is specifically:
disassembling the battery subjected to the discharge treatment in the step (2), removing the electrolyte on the surface of the working electrode, mechanically separating the working electrode from the current collector, and mechanically crushing the separated working electrode into a powder material, thereby obtaining a crude product containing the substance obtained after the active material is converted.
8. The method for preparing a pre-lithiation agent by an electrochemical process of claim 7, wherein the step (3) further comprises: and (3) separating the crude product to separate out the conductive agent and the binder, so as to obtain a refined product containing substances obtained after the active material is converted.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114335414A (en) * | 2021-11-15 | 2022-04-12 | 华中科技大学 | Method for pre-lithiation of electrode material of lithium ion battery, product and application thereof |
| CN114497549A (en) * | 2022-04-13 | 2022-05-13 | 华中科技大学 | Method for electrochemically preparing positive electrode lithium supplement material, lithium supplement material and lithium supplement slurry |
| CN115101710A (en) * | 2022-05-10 | 2022-09-23 | 清华大学 | Pre-lithiated lithium ion battery electrode and preparation system, method and application thereof |
| WO2022198662A1 (en) * | 2021-03-26 | 2022-09-29 | 宁德新能源科技有限公司 | Positive electrode lithium supplementing material, positive electrode plate containing same, and electrochemical device |
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