CN109786841B - Preparation method of lithium ion electrochemical energy storage device - Google Patents

Preparation method of lithium ion electrochemical energy storage device Download PDF

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CN109786841B
CN109786841B CN201811526450.9A CN201811526450A CN109786841B CN 109786841 B CN109786841 B CN 109786841B CN 201811526450 A CN201811526450 A CN 201811526450A CN 109786841 B CN109786841 B CN 109786841B
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lithium
pipeline
negative electrode
electrode
energy storage
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CN109786841A (en
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安亚彬
马衍伟
孙现众
张熊
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Institute of Electrical Engineering of CAS
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Institute of Electrical Engineering of CAS
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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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

The invention relates to the technical field of energy storage devices, in particular to a preparation method of a lithium ion electrochemical energy storage device, which comprises the following steps: with the negative pole and the metal lithium electrode short circuit of electricity core, and set up between electricity core and metal lithium electrode and separate diaphragm between them, with electricity core, metal lithium electrode and diaphragm encapsulate in the casing, a pre-buried at least first pipeline in the casing, carry out the heat-seal back with the casing, to the inside evacuation of casing, and pour into electrolyte into, block the intercommunication of first pipeline and second pipeline, the anodal external power supply positive pole of electricity core, the negative pole external power supply negative pole of electricity core, carry out the charge-discharge processing to the negative pole of electricity core and inlay the lithium back in advance, the charge-discharge of intercommunication anodal and negative pole, the opening of the heat-seal first pipeline other end, and break off the second pipeline and be connected with first pipeline, obtain lithium ion electrochemical energy storage device. The invention provides a preparation method of a lithium ion electrochemical energy storage device, which can be produced in a non-protective atmosphere environment, has short pre-lithium insertion time and good performance.

Description

Preparation method of lithium ion electrochemical energy storage device
Technical Field
The invention relates to the technical field of lithium ion electrochemical energy storage devices, in particular to a preparation method of a lithium ion electrochemical energy storage device.
Background
At present, domestic energy systems gradually turn from traditional fossil energy to new energy systems taking electric power as a leading factor, and in order to achieve the goal, energy storage devices are also developed towards the direction of higher energy density and lower manufacturing cost, wherein lithium ion electrochemical energy storage devices become one of the most promising directions due to high-rate discharge and longer cycle life. However, the mass production of the lithium ion electrochemical energy storage device at present has some problems, such as the inevitable lithium supplement of the negative electrode, the removal of electrolyte in a rich solution system, the removal of gas in a formation or high-pressure and high-temperature process, and the like, and all the operations need to be carried out in a protective gas environment for isolating moisture and oxygen, and are difficult to be compatible with the existing production equipment, so that the production efficiency is low.
In order to improve the energy density of the lithium ion electrochemical energy storage device, the lithium ion electrochemical energy storage device needs to be subjected to lithium pre-insertion or lithium supplement operation. However, the bottleneck of the current lithium pre-intercalation process is that the pre-intercalation time is too long, and the performance of the energy storage device needs to be improved. For example, chinese patent document CN101310350A discloses a pre-lithium insertion method in which a positive electrode, a separator, and a negative electrode are stacked, the separators are provided on the uppermost layer portion and the lowermost layer portion, four sides are fixed with tapes, and a terminal welding portion of a positive electrode current collector and a terminal welding portion of a negative electrode current collector are welded to an aluminum positive electrode terminal and a copper negative electrode terminal, respectively, by an ultrasonic welding method to obtain an electrode laminated unit; one lithium electrode is provided on each of the upper and lower portions of the electrode laminated unit, and a terminal welding portion of a lithium electrode current collector is welded to the negative electrode terminal portion by resistance welding. After the electrolyte is injected and sealed, the lithium metal is completely consumed after the lithium battery is placed for 20 days, and in addition, adverse factors such as ohmic polarization, electrochemical polarization, concentration polarization and the like exist in the electric storage device, so that the pre-lithium-embedding time is too long, and meanwhile, the battery performance is required to be improved.
Disclosure of Invention
Therefore, the technical problem to be solved by the invention is to overcome the defects that the production of the lithium ion electrochemical energy storage device in the prior art needs to be carried out in a protective gas environment for isolating water and oxygen, the production efficiency is low, the pre-lithium embedding time is long, and the performance of the lithium ion electrochemical energy storage device needs to be improved, so that the preparation method of the lithium ion electrochemical energy storage device, which can be produced in a non-protective atmosphere environment, has good compatibility with other equipment, high production efficiency, short pre-lithium embedding time and good performance of the lithium ion electrochemical energy storage device, is provided.
In order to solve the technical problem, the invention provides a preparation method of a lithium ion electrochemical energy storage device, which comprises the following steps:
the method comprises the following steps of (1) short-circuiting the negative electrode of a battery cell with a metal lithium electrode, arranging a diaphragm for separating the battery cell and the metal lithium electrode, and encapsulating the battery cell, the metal lithium electrode and the diaphragm in a shell; the negative electrode consists of a negative electrode current collector and a negative electrode active component layer arranged on the negative electrode current collector, and the thickness of the negative electrode active component layer is 20-90 microns; the positive electrode of the battery cell consists of a positive electrode current collector and a positive electrode active component layer arranged on the positive electrode current collector, and the thickness of the positive electrode active component layer is 20-180 micrometers;
at least one first pipeline is pre-buried in the shell, one end of the first pipeline is arranged in the shell, the other end of the first pipeline extends out of the shell to be communicated with a second pipeline, and the shell is subjected to heat sealing;
vacuumizing the interior of the shell through the second pipeline, injecting electrolyte, blocking the communication between the first pipeline and the second pipeline, and pre-embedding lithium into the negative electrode of the battery cell through an electrochemical method;
communicating the anode and the cathode for charging and discharging, communicating the first pipeline and the second pipeline again for air extraction, thermally sealing an opening at the other end of the first pipeline, and disconnecting the second pipeline from the first pipeline to obtain a lithium ion chemical energy storage device;
the method for pre-embedding lithium comprises the following steps:
connecting the positive electrode of the battery cell with the positive electrode of an external power supply, connecting the negative electrode of the battery cell with the negative electrode of the external power supply, performing primary discharge after primary charging as a cycle, or performing shelving after primary charging as a cycle, or performing constant-voltage charging after constant-current charging as a cycle, performing charge-discharge treatment on the negative electrode of the battery cell, and completing pre-lithium intercalation of the negative electrode of the battery cell;
the mass of the metal lithium in the metal lithium electrode is m, and the m satisfies the following formula:
m is 3.6 (A Q)/(F Z), wherein m is g, A is the metal lithium atomic weight, g/mol, F Faraday constant, Z is 1, Q is the pre-intercalation lithium capacity, which is 10-90% of the negative electrode capacity, and Q is mAh.
According to the preparation method, the aperture ratio of the copper foil with the through hole and the aperture ratio of the nickel foil with the through hole are both 2% -30%, and the aperture ratio of the aluminum foil with the through hole is 2% -30%.
In the preparation method, the circulation frequency is 1-500 times.
In the preparation method, the charging and discharging treatment is to charge the battery to the upper limit voltage by 0.01-0.5C current and lay aside for 1-24 h;
or, the charging and discharging treatment is to charge the battery to the upper limit voltage by using the current of 0.01-0.5C, and then charge the battery for 1-24h by using the upper limit voltage at constant voltage;
or, the charging and discharging treatment is to charge to the upper limit voltage with a current of 0.01-0.5C, charge for 0.1-1h with the upper limit voltage at constant voltage, discharge to the cut-off voltage with a current of 0.01-0.5C, and repeat for 1-10 times;
or, the charging and discharging treatment is to charge to the upper limit voltage with the current of 1-30C, discharge to the cut-off voltage with the current of 1-30C, and lay aside for 1-10min, and repeating the steps for 10-500 times.
In the preparation method, the upper limit voltage is 3.8-4.2V; the upper limit voltage refers to the cutoff voltage of charging; the cut-off voltage is 2.0-2.5V, preferably 2.0V.
According to the preparation method, the pre-embedded lithium amount of the negative electrode of the battery cell is 10-90% of the capacity of the negative electrode, and is preferably 75-85%; here, the open circuit potential of the negative electrode in the electrolyte solution with respect to the metallic lithium electrode is about 3.0V, and the negative electrode capacity refers to a discharge capacity in which the negative electrode is discharged from the open circuit potential to 0.01V at a current density (based on the mass of the negative electrode active component) of 25mA/g with the metallic lithium electrode as a counter electrode.
In the preparation method, the negative active component in the negative active component layer is at least one of graphite, mesocarbon microbeads, hard carbon, soft carbon, silicon monoxide and nanocrystalline silicon;
the positive active component in the positive active component layer is at least one of nickel cobalt lithium manganate, nickel cobalt lithium aluminate, lithium cobaltate, lithium iron phosphate and a porous carbon material; preferably, the porous carbon material is at least one of activated carbon, carbon aerogel or graphene; the nickel cobalt lithium manganate is also called as a ternary cathode material and can be represented by a chemical formulaLiNixCoyMnzO2Expressed that it can be classified into LiNi and LiNi according to the composition of the transition metal element1/3Co1/3Mn1/3O2、LiNi0.5Co0.2Mn0.3O2、LiNi0.6Co0.2Mn0.2O2、LiNi0.7Co0.2Mn0.1O2、LiNi0.8Co0.1Mn0.1O2And may be represented by NCM111, NCM523, NCM622, NCM721, and NCM811, respectively. The above materials are all commercially available materials.
According to the preparation method, the metal lithium electrode consists of a metal lithium electrode current collector and a metal lithium foil arranged on the metal lithium electrode current collector.
According to the preparation method, the negative current collector is a copper foil with a through hole or a nickel foil with a through hole; the positive current collector is an aluminum foil with a through hole.
The metal lithium electrode current collector is a copper foil with a through hole, a nickel foil with a through hole, a copper mesh, a nickel mesh, a foam metal copper or a foam metal nickel, and preferably the copper foil with a through hole or the copper mesh.
According to the preparation method, the battery cell is formed by sequentially laminating or winding a negative electrode, a diaphragm, a positive electrode and the diaphragm; for example, the lamination is used as the structure of the battery core: separator/negative electrode/separator/positive electrode/separator/negative electrode/separator; winding to form a structure of the battery core: separator/negative electrode/separator/positive electrode;
the battery cell is at least two in the casing, metal lithium electrode is located between the adjacent battery cell.
The preparation method comprises the steps that the electrolyte consists of lithium-containing electrolyte salt and a solvent, wherein the lithium-containing electrolyte salt is at least one of lithium hexafluorophosphate, lithium perchlorate, lithium tetrafluoroborate, lithium bis-trifluoromethanesulfonylimide and lithium difluorosulfonylimide, and the solvent is at least one of propylene carbonate, ethylene carbonate, diethyl carbonate, dimethyl carbonate and vinylene carbonate; the injection amount of the electrolyte is proper, so that the battery core is fully soaked. Electrolyte salts, solvents, lithium ion electrolytes, and separators are commercially available.
In addition, the positive electrode (positive electrode tab) and the negative electrode (negative electrode tab) were prepared as follows:
the positive electrode is prepared by coating slurry containing positive electrode active component, conductive agent and binder on aluminum foil with 2-30% open pore rate and having through holes; the negative electrode is formed by applying a slurry containing a negative electrode active ingredient, a conductive agent and a binder to a copper foil or a nickel foil having a through-hole with an open porosity of 2 to 30%. The aperture ratio refers to the ratio of the area of the holes on the current collector to the area of the current collector;
the binder is at least one of polyvinylidene fluoride (PVDF), Polytetrafluoroethylene (PTFE), sodium carboxymethylcellulose (CMC), Styrene Butadiene Rubber (SBR) or LA series aqueous binders produced by Chengdingdi Lo, and the like; the conductive agent is at least one of conductive carbon black, conductive graphite or carbon nano tubes.
According to the preparation method, the thickness of the metal lithium foil is 0.9-1.5 mm.
Further, the meaning of C is that C represents the capacity when the battery is discharged to the end voltage at a rate of 5h, that is, 1C represents a current value of 1 time the capacity, and 5C represents a current value of 5 times the capacity, according to the QB/T2502-2000 lithium ion secondary battery general Specification.
Because the metal lithium is an active element, the potential difference between the metal lithium electrode and the negative electrode in the electrolyte is large (can reach 3V), after the two electrodes are in short circuit or contact, the negative electrode and the metal lithium electrode form a pair of electrode couples, the two electrodes can perform spontaneous electrochemical reaction, lithium ions are dissolved from the metal lithium electrode and inserted between the negative electrode layers, namely under the condition of no external electric field, Li ions are inserted between the negative electrode layers+Namely, the electrolyte can diffuse to the negative electrode and the negative electrode is embedded with lithium. However, the electrochemical polarization is large in the battery cell, between the negative electrode and the metal lithium electrode, especially for the battery cell consisting of a plurality of pole pieces, and the spontaneous lithium pre-intercalation process is slow and even can reach 20 days.
The scheme of the lithium pre-intercalation method of the invention is as follows: after the metal lithium electrode is in short circuit with the negative electrode, the metal lithium is dissolved, and lithium ions enter the lithium ion electrolyte and can be diffused to the negative electrode and inserted into the active material of the negative electrode. Positive diffusion time of lithium ionThan L2and/D is in direct proportion to the square of the diffusion distance L and in inverse proportion to the diffusion coefficient D, and for the lithium ion energy storage device, under the condition of a certain diffusion distance, the diffusion time can be shortened by improving the diffusion effect. Therefore, when the pre-lithium intercalation is performed by spontaneous short circuit, an external electric field can be applied in the device by applying a charging process and a discharging process between the anode and the cathode, so that the diffusion effect is improved, and the pre-lithium intercalation time is obviously shortened. Meanwhile, after the metal lithium electrode is dissolved as a lithium source, Li+The lithium ion concentration in the electrolyte can be kept stable and unchanged when the lithium ion enters the electrolyte, the situation that the lithium ion is tried to be reduced is avoided, and the extra lithium ion is not required to be provided by adding excessive electrolyte.
According to the preparation method, the edge of the shell provided with the first pipeline is subjected to heat sealing through the first heat sealing device, and the rest edge of the shell is subjected to heat sealing through the second heat sealing device. The first heat sealing device is a sealing die provided with a groove body matched with the first pipeline, and the second heat sealing device is a heat sealing machine.
According to the preparation method, the first pipeline is a metal pipe or a plastic pipe, and the inner surface and the outer surface of the first pipeline are both coated with heat-sealing materials. The metal pipe is a stainless steel pipe, a nickel pipe or an aluminum pipe, and the plastic pipe is a PP pipe, a PET pipe or a PTFE pipe.
According to the preparation method, the material of the first pipeline is the same as that of the heat-sealing material.
According to the preparation method, the inner diameter of the first pipeline is 2-5mm, and the length of the first pipeline embedded in the shell is 5-50 mm.
The preparation method also comprises the step of separating a part of the shell containing the first pipeline from the rest of the shell.
The preparation method comprises the steps of heating at the temperature of 100-150 ℃, vacuumizing for 12-72h, and injecting the electrolyte at the pressure of-90 to-30 kPa.
The technical scheme of the invention has the following advantages:
1. according to the preparation method of the lithium ion electrochemical energy storage device, at least one first pipeline communicated with the outside is pre-buried when a pre-prepared battery core and a pre-treated lithium electrode are placed in a shell, so that after the shell is subjected to heat sealing, the shell is isolated from the outside except for an opening of the first pipeline, a series of operations such as vacuumizing, injecting electrolyte and removing redundant pregnant solution are performed on the interior of the shell through a second pipeline communicated with the first pipeline, the whole operation is always in an environment for isolating water and oxygen, the production efficiency is improved, and finally the opening of the first pipeline is subjected to heat sealing, so that the overall performance of the energy storage device is guaranteed. The preparation process is not required to be carried out in a completely sealed space, so that the preparation method is compatible with the existing production equipment, and the technical problem that the novel lithium ion electrochemical energy storage device is difficult to produce on a large scale under the existing conditions is solved.
When the negative electrode of the battery cell is in short circuit with the metal lithium electrode, the positive electrode of the battery cell is externally connected with a power supply positive electrode, the negative electrode of the battery cell is externally connected with a power supply negative electrode, and an electric field is applied to enable Li+Quickly enter into the electrolyte, and improve the diffusion effect, thereby obviously shortening the pre-lithium-intercalation time. At the same time, Li can be ensured by applying an electric field+Uniformly inserted into the active component of the negative electrode to avoid Li+A reduction in performance (e.g., capacity retention) of the lithium-ion electrochemical energy storage device due to uneven distribution in the active component of the negative electrode;
meanwhile, the specific connection mode is matched with the pre-embedded lithium amount of the negative electrode, the quality of the metal lithium in the metal lithium electrode, the thickness of the negative electrode active component layer, the thickness of the positive electrode active component layer and the like, so that the electrochemical energy storage device has a proper charge and discharge system, and the device still has high capacity retention rate after multiple charge and discharge cycles.
2. The preparation method of the lithium ion electrochemical energy storage device provided by the invention further has the advantages that the smooth proceeding of the pre-lithium embedding process is ensured, the time of the pre-lithium embedding process is shortened, and the performance (capacity retention rate) of the device is improved by controlling the parameters of the charging and discharging treatment. Meanwhile, the quality of the metal lithium in the metal lithium electrode is controlled according to a specific formula, so that the metal lithium electrode has proper amount of the metal lithium, the influence of excessive and insufficient quantity on the performance of a lithium ion electrochemical energy storage device is avoided, and finally, chemical energy is converted into electric energy and the energy is stored through the insertion and insertion of lithium ions and the ion transportation process.
3. According to the preparation method of the lithium ion capacitor, the first pipeline is reserved in the shell, a multifunctional maintenance way can be provided in the subsequent use process, and the circulation and various performances of the energy storage device can be effectively improved.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is a schematic structural diagram of a lithium-ion electrochemical capacitor according to an embodiment of the present disclosure;
FIG. 2 is a schematic diagram of a pre-lithiation process of an exemplary lithium-ion electrochemical capacitor in accordance with the present disclosure;
FIG. 3 is a graph showing the change of voltage with time during pre-intercalation of lithium in the lithium-ion electrochemical capacitor according to comparative example 1 of the present invention;
FIG. 4 is a graph showing the voltage change with time during the pre-intercalation process of the lithium-ion electrochemical capacitor in example 1 of the present invention;
FIG. 5 is a graph showing the voltage change with time during the pre-intercalation process of the lithium-ion electrochemical capacitor in example 2 of the present invention;
wherein the reference numerals are represented as:
1-a shell; 20-a metallic lithium electrode current collector; 21-metallic lithium foil; 3-a separator; 40-positive current collector; 41-positive electrode active ingredient layer; 50-a negative current collector; 51-a negative active ingredient layer; 6-positive pole tab; 7-a negative electrode tab; 8-power supply.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following detailed description, and it should be understood that the described embodiments are a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In addition, the technical features involved in the different embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
As shown in fig. 1 and 2, a negative electrode, a separator, a positive electrode and a separator are sequentially laminated or wound to form a battery core, the negative electrode is composed of a negative electrode current collector 50 and a negative electrode active component layer 51 arranged on the negative electrode current collector, for example, the negative electrode active component layer 51 can be a negative electrode coating, the thickness of the negative electrode active component layer 51 is 20-90 microns, the negative electrode current collector 50 is a copper foil with a through hole or a nickel foil with a through hole, and the opening ratios of the copper foil with a through hole and the nickel foil with a through hole are both 2% -30%; the positive electrode consists of a positive electrode current collector 40 and a positive electrode active ingredient layer 41 arranged on the positive electrode current collector, for example, the positive electrode active ingredient layer can be a positive electrode coating, the thickness of the positive electrode active ingredient layer is 20-150 microns, the positive electrode current collector is an aluminum foil with through holes, and the aperture ratio of the aluminum foil with the through holes is 2-30%;
a metal lithium electrode is placed on the outer side of the battery cell for lithium supplement, the metal lithium electrode consists of a metal lithium electrode current collector 20 and a metal lithium foil 21 arranged on the metal lithium electrode current collector, so that the metal lithium electrode is in short connection with the negative electrode, and the metal lithium electrode is separated from the battery cell by a diaphragm 3;
encapsulate electric core, metal lithium electrode and diaphragm 3 in casing 1, a pre-buried first pipeline in the casing simultaneously, inside casing was arranged in to first pipeline one end, the other end extended casing and second pipeline intercommunication. For example, sealing with an aluminum-plastic film, extending the positive electrode tab 6 and the negative electrode tab 7 out of the casing 1, sealing both sides, sealing the other side, heat-sealing the remaining side with the first pipeline through a sealing mold with a groove body, injecting a proper amount of electrolyte into the casing 1 through the second pipeline and the first pipeline to fully soak the battery cell, and then blocking the communication between the first pipeline and the second pipeline, and then connecting the positive electrode and the negative electrode with the positive electrode and the negative electrode of the power supply 8 respectively, for example, the power supply is a charge-discharge tester.
Example 1
The first pipeline is a PP pipeline with the inner diameter of 3mm and the length of 20 mm. And then, placing the heat-sealed energy storage device into hot-pressing formation equipment, controlling the temperature of the hot-pressing formation equipment to be 120 ℃, and vacuumizing the interior of the shell for 48 hours by opening a valve on the second pipeline to remove the moisture in the shell. And then, after the energy storage device is naturally cooled, injecting liquid into the shell through a second pipeline, and keeping the pressure at-70 kPa until the electrolyte is completely soaked. Then block the intercommunication of PP pipeline with the second pipeline, carry out lithium embedding in advance to the negative pole of electricity core through electrochemical method after, insert charging and discharging equipment with the positive pole, negative pole and the lithium electrode of lithium ion energy storage device at last, at first carry out charge-discharge 5 times with 50 mA's electric current to the negative pole and the lithium electrode of lithium ion energy storage device, again with 100 mA's electric current to the positive pole and the negative pole of lithium ion energy storage device charge-discharge 5 times, then communicate PP pipeline again with the second pipeline, open the second pipeline valve, carry out the degasification operation to lithium ion energy storage device through the second pipeline, heat seals the opening of the first pipeline other end, and the disconnection the second pipeline with the connection of first pipeline, obtain lithium ion electrochemical energy storage device. The lithium ion electrochemical energy storage device with the capacity of 500mAh is finally prepared under the non-protective atmosphere condition through the embodiment.
The method for pre-embedding lithium comprises the following specific steps:
stacking the diaphragms into a Z shape, separating 1 positive electrode, 1 negative electrode and 1 metal lithium electrode by using the diaphragms to prepare a laminated cell, short-connecting the negative electrode and the metal lithium electrode, injecting a proper amount of electrolyte and sealing, respectively connecting the positive electrode and the negative electrode of the lithium ion electrochemical capacitor with the positive electrode and the negative electrode of a charge and discharge tester, charging the device at a current of 0.03C, charging to 4.1V after 4.3 days, standing for 24 hours, finding that the metal lithium foil is completely dissolved after the device is disassembled, completing the pre-lithium embedding process, and sealing again to prepare the lithium ion electrochemical capacitor, as shown in figure 4;
wherein, the positive active component of the positive electrode is activated carbon, the thickness of the positive active component layer 41 is 100 microns, and the positive current collector is an aluminum foil with a through hole and an aperture ratio of 18%;
the negative active component of the negative electrode is hard carbon, the thickness of the negative active component layer 51 is 60 micrometers, and the negative current collector 50 is a copper foil with a through hole and an aperture ratio of 18%;
the metal lithium electrode is obtained by pressing and covering a metal lithium foil on a metal lithium electrode current collector, and the metal lithium electrode current collector is a copper foil with a through hole; the mass of the metal lithium foil is m, and the m satisfies the following formula: m is 3.6 (a Q)/(F Z), a is the metal lithium atomic weight, F faraday constant, Z is 1, Q is the pre-intercalation lithium capacity, m is g, Q is mAh; the pre-embedded lithium amount of the negative electrode of the battery cell is 80% of the negative electrode capacity;
LiPF with electrolyte of 1mol/L6The solvent in the electrolyte is a mixed solvent of ethylene carbonate, dimethyl carbonate and diethyl carbonate in a volume ratio of 1:1: 1.
Example 2
The first pipeline is a pipeline which has the inner diameter of 2mm and the length of 50mm and is made of the same material as the heat-seal adhesive. . And then placing the heat-sealed energy storage device into hot-pressing formation equipment, controlling the temperature of the hot-pressing formation equipment to be 100 ℃, and vacuumizing the interior of the shell for 72 hours by opening a valve on the second pipeline to completely remove the moisture in the shell. And then, after the energy storage device is naturally cooled, injecting liquid into the shell through a second pipeline, and keeping the pressure at-90 kPa until the electrolyte is completely soaked. And then blocking the communication between the first pipeline and the second pipeline, pre-embedding lithium into the negative electrode of the battery core by an electrochemical method, and finally connecting the positive electrode, the negative electrode and the lithium electrode of the lithium ion energy storage device into charging and discharging equipment, firstly charging and discharging the negative electrode and the lithium electrode of the lithium ion energy storage device for 5 times at a current of 50mA, then charging and discharging the positive electrode and the negative electrode of the lithium ion energy storage device for 5 times at a current of 100mA, then communicating the first pipeline and the second pipeline again, opening a valve of the second pipeline, performing degassing operation on the lithium ion energy storage device through the second pipeline, then sealing the opening at the other end of the first pipeline, disconnecting the second pipeline from the first pipeline, and separating a part of the shell containing the first pipeline from the rest of the shell to obtain the lithium ion electrochemical energy storage device. The lithium ion electrochemical energy storage device with the capacity of 860mAh is finally prepared under the non-protective atmosphere condition through the embodiment.
The method for pre-embedding lithium comprises the following specific steps:
stacking the diaphragms into a Z shape, separating 1 positive electrode, 1 negative electrode and 1 metal lithium electrode by using the diaphragms to prepare a laminated battery core, short-connecting the negative electrode and the metal lithium electrode, injecting a proper amount of electrolyte and sealing, respectively connecting the positive electrode and the negative electrode of the lithium ion electrochemical capacitor with the positive electrode and the negative electrode of a charge and discharge tester, charging the device to 4.1V by using 3C current, discharging the device to 2.0V by using 3C current, standing for 5 minutes, circulating for 10 times, standing the device, finding that the voltage tends to be stable, completing the electrochemical process of lithium intercalation, and sealing again to prepare the lithium ion electrochemical capacitor, as shown in figure 5;
wherein, the positive active component of the positive electrode is activated carbon, the thickness of the positive active component layer 41 is 50 microns, and the positive current collector is an aluminum foil with a through hole and an aperture ratio of 28%;
the negative active component of the negative electrode is graphite, the thickness of the negative active component layer 51 is 85 micrometers, and the negative current collector 50 is a copper foil with a through hole and an aperture ratio of 5%;
the metal lithium electrode is obtained by pressing metal lithium foil on a metal lithium electrode current collector, and the metal lithium electrode current collector is a copper mesh; the mass of the metal lithium foil is m, and the m satisfies the following formula: m is 3.6 (a Q)/(F Z), a is the metal lithium atomic weight, F faraday constant, Z is 1, Q is the pre-intercalation lithium capacity, m is g, Q is mAh; the pre-embedded lithium amount of the negative electrode of the battery cell is 80% of the negative electrode capacity;
LiPF electrolyte of 1.0mol/L6The solvent in the electrolyte is a mixed solvent of ethylene carbonate, dimethyl carbonate and diethyl carbonate in a volume ratio of 1:1: 1.
Example 3
The first pipeline is a nickel pipe, the inner diameter of which is 5mm, and the length of which is 5mm, and the outer surface and the inner surface of which are both coated with heat-sealing glue. And then placing the heat-sealed energy storage device into hot-pressing formation equipment, controlling the temperature of the hot-pressing formation equipment to be 150 ℃, and vacuumizing the interior of the shell for 12 hours by opening a valve on the second pipeline to completely remove the moisture in the shell. And then, after the energy storage device is naturally cooled, injecting liquid into the shell through a second pipeline, and keeping the pressure at minus 30kPa until the electrolyte is completely soaked. And then blocking the communication between the nickel pipe and the second pipeline, pre-embedding lithium on the anode or the cathode of the battery core by an electrochemical method, finally connecting the anode, the cathode and the lithium electrode of the lithium ion energy storage device into charging and discharging equipment, firstly charging and discharging the cathode and the lithium electrode of the lithium ion energy storage device for 5 times by 50mA current, then charging and discharging the anode and the cathode of the lithium ion energy storage device for 5 times by 100mA current, then connecting the nickel pipe and the second pipeline again, opening a valve of the second pipeline, performing degassing operation on the lithium ion energy storage device by the second pipeline, then sealing the opening at the other end of the first pipeline, and disconnecting the second pipeline from the first pipeline to obtain the lithium ion electrochemical energy storage device. Finally, the lithium ion electrochemical energy storage device with the capacity of 420mAh is prepared under the non-protective atmosphere condition through the embodiment.
The method for pre-embedding lithium comprises the following specific steps:
the difference from example 2 is that: the current for charging and discharging in the process of pre-lithium intercalation is 1C.
Example 4
The first pipeline is a stainless steel pipe with the inner diameter of 4mm and the length of 10mm, and the outer surface and the inner surface of the first pipeline are both coated with heat sealing glue. And then placing the heat-sealed energy storage device into hot-pressing formation equipment, controlling the temperature of the hot-pressing formation equipment to be 120 ℃, and vacuumizing the interior of the shell for 60 hours by opening a valve on the second pipeline to completely remove the moisture in the shell. And then, after the energy storage device is naturally cooled, injecting liquid into the shell through a second pipeline, and keeping the pressure at minus 60kPa until the electrolyte is completely soaked. And then blocking the communication between the stainless steel pipe and the second pipeline, pre-embedding lithium on the anode or the cathode of the battery core by an electrochemical method, and finally connecting the anode, the cathode and the lithium electrode of the lithium ion energy storage device into charging and discharging equipment, firstly charging and discharging the cathode and the lithium electrode of the lithium ion energy storage device for 5 times by using 100mA current, then charging and discharging the anode and the cathode of the lithium ion energy storage device for 5 times by using 300mA current, then communicating the stainless steel pipe and the second pipeline again, opening a valve of the second pipeline, performing degassing operation on the lithium ion energy storage device by using the second pipeline, then sealing the opening at the other end of the first pipeline, disconnecting the second pipeline from the first pipeline, and separating part of the shell containing the first pipeline from the rest of the shell to obtain the lithium ion electrochemical energy storage device. The lithium ion electrochemical energy storage device with the capacity of 1400mAh is finally prepared under the non-protective atmosphere condition through the embodiment.
The method for pre-embedding lithium comprises the following specific steps:
the difference from example 2 is that: the current for charging and discharging in the process of pre-lithium intercalation is 5C.
Example 5
The first pipeline is a PET pipe with the inner diameter of 2mm and the length of 20mm, and the outer surface and the inner surface of the first pipeline are both coated with heat-sealing glue. And then, placing the heat-sealed energy storage device into hot-pressing formation equipment, controlling the temperature of the hot-pressing formation equipment to be 140 ℃, and vacuumizing the interior of the shell for 25 hours by opening a valve on the second pipeline to completely remove the moisture in the shell. And then, after the energy storage device is naturally cooled, injecting liquid into the shell through a second pipeline, and keeping the pressure at minus 40kPa until the electrolyte is completely soaked. Then blocking the communication between the PET pipe and the second pipeline, pre-embedding lithium on the anode or the cathode of the battery core by an electrochemical method, finally connecting the anode, the cathode and the lithium electrode of the lithium ion energy storage device into charging and discharging equipment, firstly charging and discharging the cathode and the lithium electrode of the lithium ion energy storage device for 5 times by 50mA current, then charging and discharging the anode and the cathode of the lithium ion energy storage device for 5 times by 100mA current, then connecting the PET pipe and the second pipeline again, opening a valve of the second pipeline, performing degassing operation on the lithium ion energy storage device by the second pipeline, then sealing the opening at the other end of the first pipeline, and disconnecting the second pipeline from the first pipeline to obtain the lithium ion electrochemical energy storage device. Finally, the lithium ion electrochemical energy storage device with the capacity of 850mAh is prepared under the non-protective atmosphere condition through the embodiment.
The method for pre-embedding lithium comprises the following specific steps:
the difference from example 2 is that: the current for charging and discharging in the process of pre-lithium intercalation is 10C.
Example 6
The first pipeline is an aluminum pipe which is 5mm long and 30mm long, and the outer surface and the inner surface of the first pipeline are coated with heat sealing glue. And then placing the heat-sealed energy storage device into hot-pressing formation equipment, controlling the temperature of the hot-pressing formation equipment to be 130 ℃, and vacuumizing the interior of the shell for 30 hours by opening a valve on the second pipeline to completely remove the moisture in the shell. And then, after the energy storage device is naturally cooled, injecting liquid into the shell through a second pipeline, and keeping the pressure at-70 kPa until the electrolyte is completely soaked. And then blocking the communication between the aluminum pipe and the second pipeline, pre-embedding lithium on the anode or the cathode of the battery core by an electrochemical method, and finally connecting the anode, the cathode and the lithium electrode of the lithium ion energy storage device into charging and discharging equipment, firstly charging and discharging the cathode and the lithium electrode of the lithium ion energy storage device for 5 times at a current of 100mA, then charging and discharging the anode and the cathode of the lithium ion energy storage device for 5 times at a current of 200mA, then connecting the aluminum pipe and the second pipeline again, opening a valve of the second pipeline, performing degassing operation on the lithium ion energy storage device through the second pipeline, then sealing the opening at the other end of the first pipeline, and disconnecting the second pipeline from the first pipeline to obtain the lithium ion electrochemical energy storage device. The lithium ion electrochemical energy storage device with the capacity of 590mAh is finally prepared under the non-protective atmosphere condition through the embodiment.
The method for pre-embedding lithium comprises the following specific steps:
the difference from example 2 is that: the current for charging and discharging in the process of pre-lithium intercalation is 30C.
Example 7
The first pipeline is a PTFE pipe with the inner diameter of 5mm and the length of 40mm, and the outer surface and the inner surface of the first pipeline are both coated with heat sealing glue. And then placing the heat-sealed energy storage device into hot-pressing formation equipment, controlling the temperature of the hot-pressing formation equipment to be 110 ℃, and vacuumizing the interior of the shell for 40 hours by opening a valve on the second pipeline to completely remove the moisture in the shell. And then, after the energy storage device is naturally cooled, injecting liquid into the shell through a second pipeline, and keeping the pressure at minus 50kPa until the electrolyte is completely soaked. And then blocking the communication between the PTFE tube and the second pipeline, pre-embedding lithium on the anode or the cathode of the battery core by an electrochemical method, and finally connecting the anode, the cathode and the lithium electrode of the lithium ion energy storage device into charging and discharging equipment, firstly charging and discharging the cathode and the lithium electrode of the lithium ion energy storage device for 5 times at a current of 50mA, then charging and discharging the anode and the cathode of the lithium ion energy storage device for 5 times at a current of 200mA, then connecting the PTFE tube and the second pipeline again, opening a valve of the second pipeline, performing degassing operation on the lithium ion energy storage device through the second pipeline, then sealing an opening at the other end of the first pipeline, disconnecting the second pipeline from the first pipeline, and separating a part of the shell containing the first pipeline from the rest of the shell to obtain the lithium ion electrochemical energy storage device. The lithium ion electrochemical energy storage device with the capacity of 1800mAh is finally prepared under the non-protective atmosphere condition through the embodiment.
The method for pre-embedding lithium comprises the following specific steps:
separate with 8 positive poles, 9 negative poles with the diaphragm, make Z style of calligraphy lamination formula electricity core, combine two such lamination electricity cores and 3 metal lithium electrodes according to sandwich structure together, the concrete way is: a metal lithium electrode is clamped between the two battery cores, 1 metal lithium electrode is respectively placed on two sides of each battery core, a negative electrode is in short connection with the metal lithium electrodes, and a proper amount of electrolyte is injected and sealed; respectively connecting the anode and the cathode of the lithium ion electrochemical capacitor with the anode and the cathode of a charge-discharge tester, charging the device to 3.8V at a current of 20C, discharging the device to 2.0V at a current of 20C, standing for 5 minutes, and circulating for 300 times; then, charging the device to 4.1V by using 20C current, discharging the device to 2.0V by using 20C current, standing for 5 minutes, circulating for 200 times, finding that the metal lithium foil is completely dissolved after the device is disassembled, completing the lithium pre-embedding process, and sealing again to prepare the lithium ion electrochemical capacitor;
wherein, the positive electrode is a double-sided electrode, the positive active component is activated carbon, the thickness of the single side of the positive active component layer 41 is 120 microns, and the positive current collector is an aluminum foil with a through hole and an aperture ratio of 5%;
the negative electrode is a double-sided electrode, the negative active component is hard carbon, the thickness of one side of the negative active component layer 51 is 25 microns, and the negative current collector 50 is a nickel foil with a through hole and an aperture ratio of 28%;
the metal lithium electrode is obtained by pressing metal lithium foil on a metal lithium electrode current collector, and the metal lithium electrode current collector is a nickel net; the mass of the metal lithium foil is m, and the m satisfies the following formula: m is 3.6 (a Q)/(F Z), a is the metal lithium atomic weight, F faraday constant, Z is 1, Q is the pre-intercalation lithium capacity, m is g, Q is mAh; the pre-embedded lithium amount of the negative electrode of the battery cell is 80% of the negative electrode capacity;
LiPF with electrolyte of 1mol/L6The solvent in the electrolyte is a mixed solvent of ethylene carbonate, dimethyl carbonate and diethyl carbonate in a volume ratio of 1:1: 1.
Example 8
The first pipeline is an aluminum pipe which is 3mm long and 30mm long, and the outer surface and the inner surface of the first pipeline are coated with heat-sealing glue. And then placing the heat-sealed energy storage device into hot-pressing formation equipment, controlling the temperature of the hot-pressing formation equipment to be 140 ℃, and vacuumizing the interior of the shell for 50 hours by opening a valve on the second pipeline to completely remove the moisture in the shell. And then, after the energy storage device is naturally cooled, injecting liquid into the shell through a second pipeline, and keeping the pressure at minus 80kPa until the electrolyte is completely soaked. And then blocking the communication between the aluminum pipe and the second pipeline, pre-embedding lithium on the anode or the cathode of the battery core by an electrochemical method, and finally connecting the anode, the cathode and the lithium electrode of the lithium ion energy storage device into charging and discharging equipment, firstly charging and discharging the cathode and the lithium electrode of the lithium ion energy storage device for 5 times at a current of 100mA, then charging and discharging the anode and the cathode of the lithium ion energy storage device for 5 times at a current of 200mA, then connecting the aluminum pipe and the second pipeline again, opening a valve of the second pipeline, performing degassing operation on the lithium ion energy storage device through the second pipeline, then sealing the opening at the other end of the first pipeline, and disconnecting the second pipeline from the first pipeline to obtain the lithium ion electrochemical energy storage device. The lithium ion electrochemical energy storage device with the capacity of 630mAh is finally prepared under the non-protective atmosphere condition through the embodiment.
The method for pre-embedding lithium comprises the following specific steps:
stacking the diaphragms into a Z shape, separating 1 positive electrode, 1 negative electrode and 1 metal lithium electrode by the diaphragms to prepare a laminated cell, short-connecting the negative electrode and the metal lithium electrode, injecting a proper amount of electrolyte and sealing, respectively connecting the positive electrode and the negative electrode of the lithium ion electrochemical capacitor with the positive electrode and the negative electrode of a charge and discharge tester, charging to 4.2V at a current of 0.25C, then charging for 24h at a constant voltage of 4.2V, dismantling a device to find that the metal lithium foil is completely dissolved, completing the pre-lithium embedding process, and sealing again to prepare the lithium ion electrochemical capacitor;
wherein, the positive active component of the positive electrode is activated carbon, the thickness of the positive active component layer 41 is 50 microns, and the positive current collector is an aluminum foil with a through hole and an aperture ratio of 28%;
the negative electrode active component of the negative electrode is graphite, the thickness of the negative electrode active component layer 51 is 85 micrometers, and the negative electrode current collector 50 is a copper foil with a through hole or a nickel foil with a through hole, the opening ratio of which is 5%;
the metal lithium electrode is obtained by pressing metal lithium foil on a metal lithium electrode current collector, and the metal lithium electrode current collector is a copper mesh; the mass of the metal lithium foil is m, and the m satisfies the following formula: m is 3.6 (a Q)/(F Z), a is the metal lithium atomic weight, F faraday constant, Z is 1, Q is the pre-intercalation lithium capacity, m is g, Q is mAh; the pre-embedded lithium amount of the negative electrode of the battery cell is 85% of the negative electrode capacity;
the electrolyte is 1.5mol/L lithium tetrafluoroborate solution, and the solvent in the electrolyte is a mixed solvent of propylene carbonate, vinylene carbonate and diethyl carbonate in a volume ratio of 1:1: 1.
Example 9
The first pipeline is a PET pipe with the inner diameter of 4mm and the length of 50mm, and the outer surface and the inner surface of the first pipeline are both coated with heat-sealing glue. And then, placing the heat-sealed energy storage device into hot-pressing formation equipment, controlling the temperature of the hot-pressing formation equipment to be 130 ℃, and vacuumizing the interior of the shell for 35 hours by opening a valve on the second pipeline to completely remove the moisture in the shell. And then, after the energy storage device is naturally cooled, injecting liquid into the shell through a second pipeline, and keeping the pressure at minus 40kPa until the electrolyte is completely soaked. Then blocking the communication between the PET pipe and the second pipeline, pre-embedding lithium on the anode or the cathode of the battery core by an electrochemical method, finally connecting the anode, the cathode and the lithium electrode of the lithium ion energy storage device into charging and discharging equipment, firstly charging and discharging the cathode and the lithium electrode of the lithium ion energy storage device for 5 times by 50mA current, then charging and discharging the anode and the cathode of the lithium ion energy storage device for 5 times by 100mA current, then connecting the PET pipe and the second pipeline again, opening a valve of the second pipeline, performing degassing operation on the lithium ion energy storage device by the second pipeline, then sealing the opening at the other end of the first pipeline, and disconnecting the second pipeline from the first pipeline to obtain the lithium ion electrochemical energy storage device. The lithium ion electrochemical energy storage device with the capacity of 1200mAh is finally prepared under the non-protective atmosphere condition through the embodiment.
The method for pre-embedding lithium comprises the following specific steps:
stacking the diaphragms into a Z shape, separating 1 positive electrode, 1 negative electrode and 1 metal lithium electrode by the diaphragms to prepare a laminated cell, short-connecting the negative electrode and the metal lithium electrode, injecting a proper amount of electrolyte and sealing, respectively connecting the positive electrode and the negative electrode of the lithium ion electrochemical capacitor with the positive electrode and the negative electrode of a charge and discharge tester, charging to 3.8V at a current of 0.5C, then charging for 0.5h at a constant voltage of 3.8V, and then discharging to 2.0V at a current of 0.1C, repeating the steps for 5 times, finding that the metal lithium foil is completely dissolved after disassembling the device, completing the pre-lithium-embedding process, and sealing again to prepare the lithium ion electrochemical capacitor;
wherein, the positive active component of the positive electrode is lithium iron phosphate, the thickness of the positive active component layer 41 is 80 microns, and the positive current collector is an aluminum foil with a through hole and an aperture ratio of 22%;
the negative electrode active components of the negative electrode are mesocarbon microbeads and silica, and the mass ratio of the mesocarbon microbeads to the silica is 99.5: 0.5, the thickness of the negative active ingredient layer 51 was 30 μm, and the negative current collector 50 was a copper foil with a through-hole having an aperture ratio of 15%;
the metal lithium electrode is obtained by pressing metal lithium foil on a metal lithium electrode current collector, and the metal lithium electrode current collector is foamed metal nickel; the mass of the metal lithium foil is m, and the m satisfies the following formula: m is 3.6 (a Q)/(F Z), a is the metal lithium atomic weight, F faraday constant, Z is 1, Q is the pre-intercalation lithium capacity, m is g, Q is mAh; the pre-embedded lithium amount of the negative electrode of the battery cell is 10% of the negative electrode capacity;
the electrolyte is 0.5mol/L lithium perchlorate solution, and the solvent in the electrolyte is a mixed solvent of propylene carbonate, vinylene carbonate and ethylene carbonate with the volume ratio of 1:1: 1.
Comparative example 1
The method for pre-embedding lithium comprises the following specific steps:
1) stacking the diaphragms into a Z shape, separating 1 positive electrode, 1 negative electrode and 1 metal lithium electrode by using the diaphragms to prepare a laminated cell, short-connecting the negative electrode and the metal lithium electrode, injecting a proper amount of electrolyte and sealing to prepare the lithium ion electrochemical capacitor;
wherein, the positive active component of the positive electrode is activated carbon, the thickness of the positive active component layer 41 is 100 microns, and the positive current collector is an aluminum foil with a through hole and an aperture ratio of 18%;
the negative active component of the negative electrode is hard carbon, the thickness of the negative active component layer 51 is 60 micrometers, and the negative current collector 50 is a copper foil with a through hole and an aperture ratio of 18%;
the metal lithium electrode is obtained by pressing and covering a metal lithium foil on a metal lithium electrode current collector, and the metal lithium electrode current collector is a copper foil with a through hole; the mass of the metal lithium foil is m, and the m satisfies the following formula: m is 3.6 (a Q)/(F Z), a is the metal lithium atomic weight, F faraday constant, Z is 1, Q is the pre-intercalation lithium capacity, m is g, Q is mAh; the pre-embedded lithium amount of the negative electrode of the battery cell is 80% of the negative electrode capacity;
LiPF with electrolyte of 1mol/L6The solvent in the electrolyte is a mixed solvent of ethylene carbonate, dimethyl carbonate and diethyl carbonate in a volume ratio of 1:1: 1;
2) the voltage of the anode and the cathode is monitored by adopting a battery tester of CT2001A of Wuhanlan electric company, and the charging and discharging operation is carried out without an external charging and discharging tester, as shown in figure 3, the voltage gradually rises along with the lithium pre-intercalation process, the voltage reaches 2.8V and tends to be stable after the lithium pre-intercalation process is carried out for 10.5 days, and the lithium pre-intercalation process is finished.
The other steps are the same as in example 1.
Comparative example 2
The method for pre-embedding lithium comprises the following specific steps:
1) stacking the diaphragms into a Z shape, separating 1 positive electrode, 1 negative electrode and 1 metal lithium electrode by using the diaphragms to prepare laminated battery cores, short-connecting the negative electrodes and the metal lithium electrodes, injecting a proper amount of electrolyte and sealing to prepare a lithium ion electrochemical capacitor, and carrying out charge and discharge tests after placing for 20 days;
wherein, the positive active component of the positive electrode is activated carbon, the thickness of the positive active component layer 41 is 100 microns, and the positive current collector is an aluminum foil with a through hole and an aperture ratio of 18%;
the negative active component of the negative electrode is hard carbon, the thickness of the negative active component layer 51 is 60 micrometers, and the negative current collector 50 is a copper foil with a through hole and an aperture ratio of 18%;
the metal lithium electrode is obtained by pressing and covering a metal lithium foil on a metal lithium electrode current collector, and the metal lithium electrode current collector is a copper foil with a through hole; the mass of the metal lithium foil is m, and the m satisfies the following formula: m is 3.6 (a Q)/(F Z), a is the metal lithium atomic weight, F faraday constant, Z is 1, Q is the pre-intercalation lithium capacity, m is g, Q is mAh; the pre-embedded lithium amount of the negative electrode of the battery cell is 80% of the negative electrode capacity;
LiPF with electrolyte of 1mol/L6The solvent in the electrolyte is a mixed solvent of ethylene carbonate, dimethyl carbonate and diethyl carbonate in a volume ratio of 1:1: 1.
The other steps are the same as in example 1.
Comparative example 3
This comparative example used the lithium pre-intercalation method of example 9 in chinese patent document CN 103915262a, and the other steps were the same as in example 1.
Comparative example 4
This comparative example adopts the lithium pre-intercalation method of example 3 in chinese patent document CN 104681311a, and the other steps are the same as example 1.
Test example 1
Because a small amount of gas is generated in the process of pre-embedding lithium, the pole pieces are not tightly jointed, the electrochemical polarization is increased, and the internal resistance is increased, the devices obtained in examples 1-9 and comparative examples 1-4 are required to be subjected to one-time vacuum sealing to obtain a finished lithium ion electrochemical energy storage device, the finished lithium ion electrochemical energy storage device is subjected to charge and discharge by using 5C and 10C respectively, and the capacity retention rate is recorded, wherein the capacity retention rate is the ratio of the capacity after circulation to the initial capacity, and the circulation stability of the device is represented. The results are shown in table 1 below:
TABLE 1
Figure BDA0001904575850000231
Figure BDA0001904575850000241
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.

Claims (9)

1. A preparation method of a lithium ion electrochemical energy storage device is characterized by comprising the following steps:
the method comprises the following steps of (1) short-circuiting the negative electrode of a battery cell with a metal lithium electrode, arranging a diaphragm for separating the battery cell and the metal lithium electrode, and encapsulating the battery cell, the metal lithium electrode and the diaphragm in a shell; the negative electrode consists of a negative electrode current collector and a negative electrode active component layer arranged on the negative electrode current collector, and the thickness of the negative electrode active component layer is 20-90 microns; the positive electrode of the battery cell consists of a positive electrode current collector and a positive electrode active component layer arranged on the positive electrode current collector, and the thickness of the positive electrode active component layer is 20-180 micrometers;
at least one first pipeline is pre-buried in the shell, one end of the first pipeline is arranged in the shell, the other end of the first pipeline extends out of the shell to be communicated with a second pipeline, and the shell is subjected to heat sealing;
vacuumizing the interior of the shell through the second pipeline, injecting electrolyte, blocking the communication between the first pipeline and the second pipeline, and pre-embedding lithium into the negative electrode of the battery cell through an electrochemical method;
communicating the anode and the cathode for charging and discharging, communicating the first pipeline and the second pipeline again for air extraction, thermally sealing an opening at the other end of the first pipeline, and disconnecting the second pipeline from the first pipeline to obtain a lithium ion chemical energy storage device;
the method for pre-embedding lithium comprises the following steps:
connecting the positive electrode of the battery cell with the positive electrode of an external power supply, connecting the negative electrode of the battery cell with the negative electrode of the external power supply, performing primary discharge after primary charging as a cycle, or performing shelving after primary charging as a cycle, or performing constant-voltage charging after constant-current charging as a cycle, performing charge-discharge treatment on the negative electrode of the battery cell, and completing pre-lithium intercalation of the negative electrode of the battery cell;
the mass of the metal lithium in the metal lithium electrode is m, and the m satisfies the following formula:
m is 3.6 (A Q)/(F Z), wherein m is g, A is the metal lithium atomic weight, g/mol, F Faraday constant, Z is 1, Q is the pre-intercalation lithium capacity, which is 10-90% of the negative electrode capacity, and Q is mAh.
2. The method of claim 1, wherein the number of cycles is 1 to 500.
3. The preparation method according to claim 1, wherein the charge-discharge treatment is charging to an upper limit voltage with a current of 0.01-0.5C, and standing for 1-24 h;
or, the charging and discharging treatment is to charge the battery to the upper limit voltage by using the current of 0.01-0.5C, and then charge the battery for 1-24h by using the upper limit voltage at constant voltage;
or, the charging and discharging treatment is to charge to the upper limit voltage with a current of 0.01-0.5C, charge for 0.1-1h with the upper limit voltage at constant voltage, discharge to the cut-off voltage with a current of 0.01-0.5C, and repeat for 1-10 times;
or, the charging and discharging treatment is to charge to the upper limit voltage with the current of 1-30C, discharge to the cut-off voltage with the current of 1-30C, and lay aside for 1-10min, and repeating the steps for 10-500 times.
4. The production method according to claim 3, wherein the upper limit voltage is 3.8 to 4.2V; the cut-off voltage is 2.0-2.5V.
5. The production method according to claim 4, wherein the negative electrode active ingredient in the negative electrode active ingredient layer is at least one of graphite, mesocarbon microbeads, hard carbon, soft carbon, silica, and nanocrystalline silicon;
the positive active component in the positive active component layer is at least one of nickel cobalt lithium manganate, nickel cobalt lithium aluminate, lithium cobaltate, lithium iron phosphate and a porous carbon material;
the current collector of the metal lithium electrode is copper foil with a through hole, nickel foil with a through hole, a copper mesh, a nickel mesh, foam metal copper or foam metal nickel.
6. The method of claim 1, wherein the lithium metal electrode comprises a lithium metal electrode current collector and a lithium metal foil disposed thereon.
7. The preparation method according to claim 1, wherein the negative electrode current collector is a copper foil with through-holes or a nickel foil with through-holes; the positive current collector is an aluminum foil with a through hole.
8. The method of manufacturing of claim 1, further comprising the step of separating a portion of the housing containing the first conduit from a remaining portion of the housing.
9. The method as claimed in claim 1, wherein the heating temperature is 100-150 ℃, the time of vacuum pumping is 12-72h, and the pressure when the electrolyte is injected is-90 to-30 kPa.
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