CN112885985B - Positive pole piece and preparation method thereof, electrochemical energy storage device and pre-metallization method of electrochemical energy storage device - Google Patents

Positive pole piece and preparation method thereof, electrochemical energy storage device and pre-metallization method of electrochemical energy storage device Download PDF

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CN112885985B
CN112885985B CN202110134865.7A CN202110134865A CN112885985B CN 112885985 B CN112885985 B CN 112885985B CN 202110134865 A CN202110134865 A CN 202110134865A CN 112885985 B CN112885985 B CN 112885985B
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energy storage
storage device
electrochemical energy
lithium
pole piece
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CN112885985A (en
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纪效波
邹康宇
邹国强
侯红帅
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Shenzhen Jingong Energy Co ltd
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Central South University
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Abstract

The invention provides a positive pole piece and a preparation method thereof, an electrochemical energy storage device and a pre-metallization method of the electrochemical energy storage device, wherein the positive pole piece comprises a metal current collector and a positive active material layer attached to the metal current collector, the positive active material layer comprises 30-80% of a positive active material, 0-60% of an additive, 5-15% of a binder and 5-15% of a conductive agent in percentage by mass, the additive is organic carboxylate with a structure shown in a formula I, and R- (COOM) n (formula I); wherein R is one of H, phenyl or saturated or unsaturated alkyl with 1 or 2 carbon atoms, and M is any one of Li, Na and K; n is 1-6 and n is a natural number; the dosage of the additive is more than 0. The positive pole piece is applied to an electrochemical energy storage device, so that the electrochemical energy storage device has excellent electrochemical performance and good cycle stability.

Description

Positive pole piece and preparation method thereof, electrochemical energy storage device and pre-metallization method of electrochemical energy storage device
Technical Field
The invention relates to the relevant technical field of electrochemical energy storage devices, in particular to a novel pre-metallization strategy for an electrochemical energy storage device based on a Kolbe decarboxylation reaction, and relates to a pre-lithiation and pre-sodium treatment method for a secondary ion battery and a method for constructing an alkali metal ion capacitor for pre-lithiation, pre-sodium treatment and pre-potassium treatment; more particularly, the invention relates to a positive pole piece and a preparation method thereof, an electrochemical energy storage device and a pre-metallization method of the electrochemical energy storage device.
Background
With the development of society and the advancement of science and technology, how to develop an electrochemical energy storage device with good safety, high energy density, high power density and long cycle stability is a major issue to be solved urgently in the future. With the deep research of electrode materials, the improvement of the manufacturing level and the improvement of the requirements of the market on energy storage devices, the improvement of the performance of the energy storage devices through the traditional ideas of replacing the electrode materials and developing new electrolyte is very limited. The appearance of the pre-lithiation technology provides an effective solution for improving the performance of an energy storage system, particularly improving irreversible capacity loss and improving energy density, and injects new activity for the development of an electrochemical energy storage technology.
Currently, the prelithiation of the negative electrode can be achieved by elemental lithium metal. However, metal lithium as one of alkali metal elements has extremely active chemical properties and extremely high potential safety hazards. Therefore, the operation of prelithiation of elemental metal lithium needs to be performed in a highly inert environment in a glove box. Subsequently, FMC Lithium corporation, USAA Stabilized Lithium Metal Powder (SLMP) is disclosed, which is a prelithiation reagent that can be commercially produced and used. SLMP is prepared from core-shell type fine particle powder, metallic lithium powder (97 wt.%) and Li (3 wt.%) 2 CO 3 And (4) forming. Wherein Li 2 CO 3 The lithium ion battery can be used as a protective film to be uniformly coated on the surface of lithium particles, so that harmful side reactions can be effectively prevented. The defects that SLMP is expensive, the prelithiation process is usually carried out in a naked environment, dust is easily caused, the environment is polluted, and potential safety hazards exist.
Therefore, the development of a controllable, large-scale and standardized prelithiation technology can effectively and accurately compensate the capacity of the high specific volume electrode, and is very important for the development of energy storage systems such as lithium ions, lithium sulfur, lithium air batteries, lithium ion capacitors and the like. Since the metallic lithium source is abundant and low in the earth crust, the future development of the lithium ion-based energy storage device is greatly limited. And because the sodium ions and the potassium ions have similar physical and chemical properties and abundant storage capacity with lithium ions, the corresponding sodium/potassium ion-based energy storage device has better commercialization prospect. However, because the metal sodium and the metal potassium have low melting points and extremely active chemical properties, and can react with water to generate hydrogen, potential safety hazards are caused, and the development of the sodium/potassium ion-based energy storage device is in a bottleneck at present. At present, an efficient pre-sodium treatment and pre-potassium treatment technology is urgently needed to simplify the construction of a sodium/potassium ion-based energy storage device, which is beneficial to commercial production and application. In addition, the problems of further reducing the pre-metallization cost, improving the safety of the pre-metallization and reducing the pollution of the pre-metallization to the environment are also the current urgent solutions.
Disclosure of Invention
In order to solve the above technical problems in the prior art, an object of the present invention is to provide a positive electrode sheet containing a low molecular weight organic carboxylate, which is applied to an electrochemical energy storage device, and can utilize the low molecular weight organic carboxylate to implement efficient and safe pre-metallization on a negative electrode through kolbe decarboxylation reaction, so as to obtain an electrochemical energy storage device with excellent electrochemical performance and good cycle stability. The universality of the Kolbe decarboxylation reaction is not only suitable for the pre-lithiation of the organic lithium carboxylate, but also suitable for the pre-sodium treatment and the pre-potassium treatment of the organic sodium carboxylate and the organic potassium carboxylate respectively.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a positive pole piece comprises a metal current collector and a positive active material layer attached to the metal current collector, wherein the positive active material layer comprises 30-80% of a positive active material, 0-60% of an additive, 5-15% of a binder and 5-15% of a conductive agent in percentage by mass, and the additive is organic carboxylate with a structure shown in a formula I;
r- (COOM) n (formula I);
wherein R is H, phenyl or saturated or unsaturated alkyl with 1 or 2 carbon atoms, and M is any one of Li, Na and K; n is 1-6 and n is a natural number; the dosage of the additive is more than 0.
In some embodiments, the positive active material layer includes 40% to 60% of a positive active material, 15% to 40% of an additive, 5% to 15% of a binder, and 5% to 15% of a conductive agent.
In some embodiments, the organic carboxylate salt comprises at least one of lithium acetate, lithium formate, lithium propionate, lithium lactate, lithium oxalate, lithium acrylate, lithium benzoate or sodium acetate, sodium formate, sodium propionate, sodium lactate, sodium oxalate, sodium acrylate, sodium benzoate or potassium acetate, potassium formate, potassium propionate, potassium lactate, potassium oxalate, potassium acrylate, potassium benzoate; wherein, when more than one organic carboxylate is added into the anode material, only the organic carboxylate containing the same metal element is added. Specifically, when the positive pole piece is used for preparing a secondary lithium ion battery or a lithium ion capacitor, the additive is organic lithium carboxylate; when the positive pole piece is used for preparing a secondary sodium ion battery or a sodium ion capacitor, the additive is organic sodium carboxylate; when the positive pole piece is used for preparing the potassium ion capacitor, the additive is organic potassium carboxylate.
In some embodiments, the positive active material is an organic compoundA material capable of intercalating/deintercalating lithium, sodium or potassium ions, including, but not limited to, any one of lithium iron phosphate, lithium cobalt oxide, lithium nickel oxide, lithium manganese oxide, sodium rich phase oxide, sodium deficient phase oxide, polyanionic oxide, prussian blue analog, and activated carbon. Specifically, the lithium manganese lithium iron phosphate, lithium cobaltate, lithium manganate, lithium nickel cobalt manganese ternary material, Na 2 RuO 3 ，Na 2 Mn 3 O 7 、P2-Na 2/3 Ni 1/3 Mn 2/3-x Ti x O 2 ，P2-Na 2/3 Ni 1/3 Mn 2/3 O 2 、Na 3 V 2 (PO 4 ) 3 ，Na 2 FeP 2 O 7 And the like.
In some embodiments, the metal current collector includes, but is not limited to, copper foil, aluminum foil, and the like.
The second purpose of the present invention is to provide a method for preparing the above positive electrode plate, wherein the positive electrode plate is prepared by one of the following methods:
uniformly mixing the positive electrode active material, the additive, the binder and the conductive agent to form slurry, coating the slurry on the surface of the metal current collector, and drying to obtain the metal current collector;
uniformly mixing the positive active material, the binder and the conductive agent in proportion to form slurry, then coating the slurry on the surface of the metal current collector, and drying to form an active material layer; and then coating the additive on the surface of the active material layer in a spraying or coating mode according to a proportion, standing and drying to obtain the active material.
The invention also provides an electrochemical energy storage device, which comprises the positive pole piece in any one of the above embodiments.
In some embodiments, the electrochemical energy storage device further comprises a negative electrode, an electrolyte, and a separator. The anode, the cathode, the electrolyte and the diaphragm are correspondingly configured and assembled according to actual requirements in a conventional mode in the field to form the electrochemical energy storage device. Specifically, if a secondary lithium ion battery is prepared, the positive electrode materialThe additive is lithium iron phosphate, lithium cobaltate, lithium manganate, lithium nickel cobalt manganese oxide ternary material and the like, and the additive is organic lithium carboxylate; if a secondary sodium ion battery is prepared, the positive electrode material is a sodium-rich phase oxide, such as Na 2 RuO 3 ，Na 2 Mn 3 O 7 Etc.; sodium-deficient oxides, e.g. P2-Na 2/3 Ni 1/3 Mn 2/3-x Ti x O 2 ，P2-Na 2/3 Ni 1/ 3 Mn 2/3 O 2 Etc.; polyanionic oxides, e.g. Na 3 V 2 (PO 4 ) 3 ，Na 2 FeP 2 O 7 And prussian blue analogue, etc., the additive is organic carboxylic acid sodium salt; if the alkali metal ion capacitor is prepared, the positive electrode material is activated carbon, and the additive can be organic lithium carboxylate, sodium carboxylate and potassium carboxylate respectively.
In some embodiments, the electrochemical energy storage device is a lithium ion capacitor, a lithium ion battery, a sodium ion capacitor, a sodium ion battery, and a potassium ion capacitor.
The fourth purpose of the invention is to provide a pre-metallization method of an electrochemical energy storage device, which comprises the following steps:
s1, uniformly mixing the positive active material, the additive, the first binder and the first conductive agent to form positive slurry, coating the positive slurry on the surface of the metal current collector, and drying to prepare a positive electrode;
s2, uniformly mixing the negative electrode active material, the second binder and the second conductive agent to form negative electrode slurry, coating the negative electrode slurry on the surface of the metal current collector, and drying to prepare a negative electrode;
s3, assembling the positive electrode and the negative electrode manufactured in the S1 and the S2, the electrolyte and the diaphragm into an electrochemical energy storage device, performing charge and discharge for at least one cycle under the voltage of 2.0-4.5V, and standing to obtain the electrochemical energy storage device capable of being normally used;
wherein, in step S1, the additive is the organic carboxylate according to claim 1, and the positive electrode active material is activated carbon; in step S2, the negative electrode active material is any one of anatase, graphite, porous carbon, or a metal oxide.
In some embodiments, the positive electrode slurry includes, by mass percentage, 40% to 60% of a positive electrode active material, 15% to 40% of an additive, 5% to 15% of a first binder, and 5% to 15% of a first conductive agent.
In some embodiments, the negative electrode slurry includes 70% to 90% of a negative electrode active material, 5% to 15% of a second binder, and 5% to 15% of a second conductive agent, by mass percentage.
The binder, the first binder and the second binder can be respectively selected from at least one of polyvinylidene fluoride, polyvinylidene fluoride-hexafluoropropylene, polytetrafluoroethylene and polyurethane; the conductive agent, the first conductive agent and the second conductive agent can be at least one of graphite, acetylene black, conductive carbon black, superconducting carbon black and carbon nano tubes respectively.
Compared with the prior art, the invention has the following beneficial effects:
the organic carboxylate with small relative molecular mass is used as an additive, and is mixed with a common positive electrode material, a binder and a conductive agent of an electrochemical energy storage device and then attached to the surface of a metal current collector to prepare the positive electrode plate. The positive pole piece added with the micromolecular organic carboxylate is applied to a metal ion battery, when the first charge-discharge circulation is carried out, the organic carboxylate in the positive pole material is subjected to a Colerb decarboxylation reaction, the reaction mechanism is shown in figure 1, the micromolecular organic carboxylate is decomposed into metal ions, carbon dioxide and free radicals, the metal ions are embedded into a negative active substance, the carbon dioxide is gas and can be directly discharged out of a reaction system, and the free radicals are coupled to generate micromolecular hydrocarbon substances or water; if R is a hydrocarbon group with 1 or 2 carbon atoms, coupling occurs between free radicals to generate a small molecular hydrocarbon substance, the small molecular hydrocarbon substance is a gas, and metal ions can be embedded into a negative electrode material, so that the pre-metallization of a negative electrode is realized, and the electrochemical performance of the metal ion battery is improved; therefore, after the organic carboxylate is subjected to the Kolbe decarboxylation reaction, except for generating metal ions, other products are gas or water, the gas can be directly discharged out of a reaction system and cannot be remained in the electrolyte, and a small amount of water generated by the reaction is directly dissolved in the electrolyte and does not influence the electrolyte. Therefore, the use of the organic carboxylate not only improves the electrochemical performance of the secondary metal ion battery, but also is beneficial to the subsequent long-term cycling stability of the metal ion battery.
The positive pole piece added with the small-molecule organic carboxylate is used for preparing a metal ion capacitor, after the positive pole piece, the negative pole piece, electrolyte and a diaphragm are assembled into the metal ion capacitor, before the capacitor is used, charging and discharging circulation is firstly carried out to realize the pre-metallization of the negative pole piece, in the pre-metallization process, the organic carboxylate is subjected to a Kolbe decarboxylation reaction to generate a hydrocarbyl group, carbon dioxide and free metal ions, the hydrocarbyl group is subjected to free coupling to form small-molecule hydrocarbon gas, the reaction system is directly discharged when the carbon dioxide is generated, and the metal ions are dissociated and embedded into a negative pole material to realize the pre-metallization of a negative pole.
The positive pole piece provided by the invention is applied to an electrochemical energy storage device, can effectively realize negative pole premetallization, obtains the electrochemical energy storage device with excellent electrochemical performance and good circulation stability, and can avoid the problem that the subsequent use of the electrochemical energy storage device is influenced by excessive impurity doping of electrolyte. In addition, the preparation method of the positive pole piece is convenient to operate, can be carried out under the external atmospheric condition, does not need to be carried out in a specific anhydrous and oxygen-free environment, is safe and effective, and can enlarge the application range of the organic carboxylate
According to the pre-metallization method of the electrochemical energy storage device, provided by the invention, organic carboxylate is used as an additive of the anode material, in the pre-lithiation process, except for dissociated metal ions, generated other substances are all gases and are directly discharged out of a reaction system, so that the anode can be effectively pre-metallized, and the prepared electrochemical energy storage device has excellent electrochemical performance and good long-term cycling stability.
The pre-metallization method of the invention completes the pre-metallization process of the cathode in one step, has simple operation, short period and low cost, and meets the requirement of industrial production; the prepared electrochemical energy storage device has good electrochemical performance and excellent cycling stability.
Drawings
FIG. 1 is a schematic diagram of the reaction mechanism of pre-lithiation of lithium acetate during charging and discharging of the electrochemical energy storage device made in example 1;
FIG. 2 shows the positive electrode sheet of example 1 at 5mV s -1 CV plot at scan speed;
FIG. 3 shows the positive electrode plate of example 1 at 100mA g -1 GCD plot at current density;
FIG. 4 is an ex situ X-ray powder diffraction pattern of the positive electrode sheet of example 1 before and after cycling;
FIG. 5 is a GCD graph of (a) graphite// LFP and (b) graphite// LFP/AC-Li LIBs; (c) energy density comparison plots and (d) cycling stability plots for the graph// LFP and the graph// LFP/AC-Li LIBs;
FIG. 6 is (a) graph of CV activation for a lithium ion capacitor assembled from graphite// APC/AC-Li LIC; (b) CV diagrams for different scanning speeds of graph// APC/AC-Li LIC; (c) GCD plots at different current densities for graphite// APC/AC-Li LIC; (d) ragon comparison plots for graph// APC/AC-Li LIC and pre-lithiated graph// APC LIC;
in FIG. 7, (a) TiO 2 V/APC/AC-Li LIC assembled lithium ion capacitor CV activation diagram; (b) TiO 2 2 V/CV diagrams at different scanning speeds of APC/AC-Li LIC; (c) TiO 2 2 // GCD plot at different current densities of APC/AC-Li LIC; (d) TiO 2 2 // APC/AC-Li LIC and pre-lithiated TiO 2 Comparative Ragon plot for APC LIC;
FIG. 8 is an XRD pattern of the electrolyte after cycling with and without lithium acetate added to the positive electrode plate;
FIG. 9 is an XRD pattern of the electrolyte after prelithiation treatment of the half cell made in comparative example 1;
FIG. 10 is a GCD diagram of (a) NHPC-800// NMT and (b) NHPC-800// NMT/AC-Na SIBs; (c) cycling stability plots for NHPC-800// NMT and NHPC-800// NMT/AC-Na SIBs;
in FIG. 11, (a) NHPC-800// APC/AC-Na SIC and pre-modified NRagon comparison graph of HPC-800// APC SIC; (b) TiO 2 2 // APC/AC-Na SIC and pre-conditioned TiO 2 Comparative Ragon plot for APC SIC;
FIG. 12 is a Ragon comparison of NHPC-800// APC/AC-K KIC and pre-assigned NHPC-800// APC KIC.
Detailed Description
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein, but rather should be construed as broadly as the present invention is capable of modification in various respects, all without departing from the spirit and scope of the present invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
Example 1
1. Preparation of positive pole piece
(1) Preparation of lithium acetate (AC-Li) positive pole piece
Placing lithium acetate, a binder PVDF, a conductive agent SuperP and a small amount of N-methylpyrrolidone in an agate mortar, carefully grinding until the slurry is uniform, coating the obtained uniform slurry on an Al foil, and drying in vacuum for 12 hours at 80 ℃ to obtain a positive pole piece; wherein, the content of lithium acetate is 60 percent, the content of PVDF is 10 percent and the content of SuperP is 30 percent by mass percentage.
(2) Preparation of lithium iron phosphate/lithium acetate (LFP/AC-Li) positive pole piece
The preparation method of the LFP/AC-Li positive pole piece is the same as that of the AC-Li positive pole piece, and the difference is that the lithium iron phosphate content is 60%, the lithium acetate content is 20%, the PVDF content is 10% and the Super P content is 10% in percentage by mass.
(3) Sodium deficient phase sodium anode oxide/sodium acetate (P2-Na) 2/3 Ni 1/3 Mn 2/3-x Ti x O 2 Preparation of/AC-Na) positive pole piece
P2-Na 2/3 Ni 1/3 Mn 2/3-x Ti x O 2 The preparation method of the/AC-Na positive pole piece is the same as that of the AC-Na positive pole piece, and the difference is that the P2-Na is calculated by mass percentage 2/3 Ni 1/3 Mn 2/3-x Ti x O 2 (i.e., NMT) content of 60%, sodium acetate content of 20%, PVDF content of 10%, Super P content of 10%.
(4) Preparation of active carbon/lithium acetate (APC/AC-Li) anode piece
The preparation method of the APC/AC-Li positive pole piece is the same as that of the AC-Li positive pole piece, and the difference is that the content of the activated carbon and the lithium acetate is 40 percent, the content of the PVDF is 10 percent, and the content of the Super P is 10 percent according to the mass percentage.
(5) Preparation of active carbon/sodium acetate (APC/AC-Na) and active carbon/potassium acetate (APC/AC-K) positive pole piece
The preparation method of the APC/AC-Na and APC/AC-K positive pole piece is the same as that of the APC/AC-Li positive pole piece, and the difference is that under the condition of not changing the mass percentage ratio, sodium acetate and potassium acetate are used for replacing lithium acetate.
2. Preparation of negative pole piece
Making the negative active material anatase TiO 2 Mixing sodium carboxymethylcellulose serving as a binder and a conductive agent Super P to serve as a negative electrode material, placing the mixture and a small amount of distilled water in an agate mortar, carefully grinding the mixture until the slurry is uniform, coating the obtained uniform slurry on a Cu foil, and performing vacuum drying for 12 hours at the temperature of 80 ℃ to obtain a negative electrode piece; the negative electrode material comprises the following components in percentage by mass: anatase TiO 2 70 percent, 15 percent of sodium carboxymethyl cellulose and 15 percent of Super P.
3. Electrochemical performance test
Respectively manufacturing a positive pole piece, a negative pole piece and a diaphragm which are reasonable in thickness and proper in size, and assembling the positive pole piece, the negative pole piece, the diaphragm and the electrolyte into a half-cell in a glove box by using a CR2016 battery case and other accessories; wherein, the positive pole piece is prepared by the above method, the negative pole piece is prepared by the above method, and the electrolyteIs 1mol/L LiPF 6 Electrolyte with volume ratio of 1:1:1 of ethylene carbonate, methyl ethyl carbonate and dimethyl carbonate and 1mol/L of NaClO 4 Electrolyte with volume ratio of 1:1:1 of ethylene carbonate, ethyl methyl carbonate and dimethyl carbonate and 0.8mol/L KPF 6 Electrolyte with volume ratio of 1:1 of ethylene carbonate and dimethyl carbonate, a diaphragm of Whatman GF/C glass fiber membrane, and a CR2016 battery case is selected for assembly in a glove box.
And (3) constructing the lithium ion battery by using the cut negative graphite and a lithium iron phosphate positive electrode or a lithium iron phosphate/lithium acetate composite positive electrode according to a certain mass ratio (conventional ratio in the field).
Cutting the negative pole NHPC-800 porous carbon material and P2-Na 2/3 Ni 1/3 Mn 2/3-x Ti x O 2 Positive electrode or P2-Na 2/3 Ni 1/3 Mn 2/3-x Ti x O 2 The lithium acetate composite positive electrode is used for constructing a sodium-ion battery according to a certain mass ratio (a conventional ratio in the field).
And constructing a novel mixed ion capacitor by using the cut negative electrode and the active carbon/acetate composite positive electrode according to a certain mass ratio. The constructed novel mixed ion capacitor adopts a cyclic volt-ampere (CV) test method, and the scanning speed is 5mV s -1 The voltage interval of 2-4.5V is scanned for 5 turns and a specific voltage above 4.0V must be reached. After the scanning is finished and the standing is carried out for 12 hours, the in-situ pre-metallization process can be realized.
As shown in FIG. 2, after the half-cell system was subjected to charge-discharge cycles, the ratio of Li/Li was adjusted to Li/Li + In terms of potential, the first CV plot of lithium acetate shows an anodization peak at 4.49V, which corresponds to a lithium ion delimination peak in lithium acetate, while the subsequent second CV cycle does not show the corresponding anodic peak of the first cycle, indicating that the delithiation reaction of lithium acetate is irreversible and that the delithiated lithium ions cannot return to the original species itself. The reason is that lithium acetate is subjected to Kolbe decarboxylation reaction and is decomposed into ethane, carbon dioxide and lithium ions, the ethane and the carbon dioxide obtained after the reaction are separated from the reaction system in the form of gas and can not be reacted again to be changed into lithium acetate, the forward progress of the reaction is promoted, and the score is simultaneously obtainedThe dissociated lithium ions are changed into free lithium ions. Meanwhile, as can be seen from FIG. 3, the specific charge capacity of the first coil is about 349.9mAh g -1 The de-lithiation oxidation potential is 4.04V, the first-circle discharge specific capacity is rapidly reduced to be only 23.4mAh & g -1 Further, it is explained that the elimination reaction of lithium acetate is irreversible and the elimination reaction has a high capacity. Thus, lithium acetate is an objective prelithiation additive, and further, lithium organic carboxylate is a novel and considerable prelithiation additive based on the kolbe decarboxylation reaction principle.
To further illustrate the irreversibility of the lithium acetate reaction, applicants performed characterization analysis on the cycled positive electrode sheet by ex situ X-ray powder diffraction testing, with the results shown in fig. 4. As shown in fig. 4, the XRD pattern of the cycled positive electrode sheet was in the range of 5 ° to 35 ° and the characteristic peak of lithium acetate was significantly small, indicating that the reaction was irreversible.
In addition, the electrolyte before and after circulation is respectively carried out 13 The results of the C nuclear magnetic test are shown in fig. 8. As shown in fig. 8, no new peak was generated in the electrolyte after the cycling, and the test results were the same as those of the electrolyte before the cycling, indicating that after the cycling, the pre-lithiation was completely achieved and no new species was generated and dissolved in the electrolyte. After circulation, the lithium acetate is decomposed into butane and carbon dioxide which are discharged out of the system in a gas form, so that the performance stability of the electrolyte is ensured, and the performance stability of the half-cell is further ensured.
In order to verify the practical application of lithium acetate in an electrochemical energy storage system, a lithium ion battery and a lithium ion capacitor are respectively prepared, and the pre-lithiation effect and the battery performance are judged, specifically as follows:
(1) preparation and testing of lithium ion batteries
Lithium iron phosphate (LFP) material is used as a positive electrode active material, commercialized negative electrode active material graphite is used as a negative electrode, electrolyte and a diaphragm are assembled to obtain the lithium ion battery, and lithium acetate is used as a positive electrode additive to be introduced into a graphite/LFP lithium ion battery system to evaluate the pre-lithiation effect. Correlation of performance of assembled lithium ion batteriesThe test results are shown in fig. 5. As shown in the graphs a and b of FIG. 5, the specific capacity of the first charge is from 156.4mAh g -1 Increased to 192.3mAh g -1 The lithium acetate in the positive pole piece is decomposed to provide a redundant additional lithium source for the negative graphite; in addition, as shown in the graph c of FIG. 5, the energy density of the battery system was from 333.9 Wh.kg -1 Lifting to 360.9Wh kg -1 Fig. 5 d shows that the battery system with lithium acetate added to the positive electrode maintains excellent performance and good cycle stability, which indicates that lithium acetate can improve the overall energy density of the lithium ion battery system and make the lithium ion battery system have excellent cycle stability, so that the lithium ion battery exhibits excellent electrochemical performance.
(2) Preparation and testing of lithium ion capacitors
The APC/AC-Li positive pole piece is used as the positive pole, and the commercialized graphite and anatase TiO are used 2 The negative pole piece is used as a negative pole, and the lithium ion capacitor is assembled by the electrolyte and the diaphragm; a cyclic voltammetry test is selected, and specifically comprises the following steps: at a scanning speed of 5mV s -1 Scanning for 5 circles in a voltage interval of 2.0-4.5V and necessarily reaching a specific voltage more than 4.0V, and standing for 12 hours after scanning. The lithium ion capacitor after cycling was subjected to the relevant performance tests, and the test results are shown in fig. 6, where fig. 6 is a CV diagram of the initial prelithiation activation process. As can be seen from fig. 6, the CV area of the first turn is much larger than that of the second turn, and the first turn has a distinct oxidation peak at about 2.5V, which indicates that the lithium ion capacitor system has an irreversible detachment reaction in the first turn cycle, and a lithium ion capacitor with normal electrochemical behavior is obtained after the detachment reaction. After the circulation and standing, the open-circuit voltage of the lithium ion capacitor is about 1V (before the circulation, the open-circuit voltage is about-0.03V), which shows that after the circulation, lithium acetate in the anode removes lithium ions and moves to the cathode material, and an effective prelithiation process is realized, so that the normally used ion capacitor is obtained. Fig. 6 a and b are CV curves and constant current charge and discharge curves of cyclic voltammetry charge and discharge, respectively, and it can be seen from fig. 6 a and b that two energy storage mechanisms of faradaic behavior and faradaic behavior exist in the lithium ion capacitor system. In addition, lithium ions after voltammetric cyclingThe energy density of the capacitor reaches 41.27Wh kg -1 (the energy density after half-cell prelithiation treatment was 48.57 Wh. kg -1 ) The method that after lithium acetate is used as a positive electrode additive to prepare the lithium ion capacitor in the lithium ion capacitor body system, the lithium ion capacitor with excellent electrochemical performance can be prepared by the method that the pre-lithiation treatment is performed circularly is also applicable.
To extend the suitability of lithium acetate as a prelithiation additive, commercial anatase TiO was also selected 2 As a negative electrode, preparing a lithium ion capacitor by taking an AC-Li positive pole piece as a positive electrode, and then performing cyclic voltammetry at a scanning speed of 5mV s -1 Scanning for 5 circles in a voltage interval of 2.0-4.5V and necessarily reaching a specific voltage more than 4.0V, and standing for 12 hours after scanning. The lithium ion capacitor after cycling is subjected to related performance tests, and the test results are shown in fig. 7. As shown in FIG. 7, with anatase TiO 2 In the lithium ion capacitor system as the negative electrode, in-situ pre-lithiation process is performed after circulation, so that TiO is realized 2 The material is pre-lithiated, and the lithium ion capacitor has excellent electrochemical performance, which shows that the preparation method provided by the invention has universality and can be suitable for graphite and anatase TiO 2 And the electrochemical energy storage device subjected to circulation is excellent in performance, not only has good charge and discharge performance, but also has good circulation stability.
In order to expand the adaptability of the method, sodium acetate and potassium acetate are selected as pre-sodium treatment and pre-potassium treatment additives respectively to prepare the positive pole piece. As shown in FIG. 10, sodium acetate was introduced into NHPC-800// P2-Na as a positive electrode additive 2/3 Ni 1/3 Mn 2/3-x Ti x O 2 In the (NHPC-800// NMT) sodium-ion battery system, the energy density and the cycling stability of the NHPC-800// NMT/AC-Na are obviously improved. After 50 cycles, the performance of the NHPC-800// NMT sodium ion cell without sodium acetate addition was only 28.5% retained, while the performance of NHPC-800// NMT/AC-Na after 50 cycles of sodium acetate addition was stable at 79.9% of the initial capacity. As shown in FIGS. 11 and 12, sodium acetate and potassium acetate were added to the activated carbon material to construct a structureThe sodium ion capacitor and the potassium ion capacitor have excellent performance, good charge and discharge performance and good cycle stability. The preparation method provided by the invention has universality and can be suitable for various electrochemical energy storage device systems.
Comparative example 1
1. Preparation of positive pole piece
A positive electrode sheet was prepared in the manner of preparing an AC-Li positive electrode sheet in example 1, except that in this comparative example, lithium rosmarinate was selected as the positive electrode active material.
The positive pole piece prepared in the comparative example, the negative pole piece prepared in the example 1, the diaphragm and the electrode solution are assembled into a half-cell, wherein the electrolyte is 1mol/L LiPF 6 The electrolyte with the volume ratio of 1:1:1 is ethylene carbonate, methyl ethyl carbonate and dimethyl carbonate, and the diaphragm is a Whatman GF/C glass fiber membrane. And (3) testing the assembled half cell by Cyclic Voltammetry (CV), specifically: at a scanning speed of 5mV s -1 Scanning for 5 circles in a voltage range of 2.0-4.5V, and standing for 12 hours after the scanning is finished.
The circulated electrolyte of the half cell is carried out 13 And C, performing nuclear magnetic test, wherein a test result is shown in FIG. 9, a new peak is generated in the electrolyte, which indicates that after circulation, lithium ions are removed from the lithium rosette salt to obtain lithium ions and cyclohexadecanone products, the lithium ions are embedded into the negative electrode material, the products directly remain in the electrolyte, and residues in the electrolyte can have certain influence on the subsequent use of the electrolyte, so that the stability of the electrolyte is greatly influenced, and the electrochemical performance and the circulation stability of the lithium ion battery or the lithium ion capacitor are further influenced.
In the application, the micromolecular organic carboxylate is used as an additive of a complementary metal source (such as Li, Na and K) to be applied to the positive pole piece, the separation of metal ions is realized and the pre-metallization of the negative pole is realized based on the Kolbe decarboxylation reaction principle, so that the safety of the pre-metallization is improved, the pre-metallization cost is reduced, and the pollution of the pre-metallization to the environment is reduced; besides the fact that the micromolecular organic carboxylate can dissociate metal ions to achieve negative electrode pre-metallization, other generated products have no influence on the electrolyte, or water is generated to be dissolved in the electrolyte, the generated water is negligible compared with the amount of the electrolyte, or generated gas is directly discharged out of a system, no residue exists in the electrolyte, and the subsequent normal use of the electrolyte is not influenced. The application selects the micromolecular organic carboxylate as the metal ion supplement additive to be applied to the positive pole piece, so that the premetallization of the negative pole can be realized, the effect of a good metal source supplement is achieved, the electrolyte is not affected, and the electrochemical energy storage device has better electrochemical performance and long-term circulation stability.
The scheme of this application is applicable to the electrochemistry energy memory of different systems, including lithium ion secondary battery, lithium ion capacitor, sodium ion secondary battery, sodium ion capacitor and potassium ion capacitor, can be according to actual demand on the basis of the corresponding electrochemistry energy memory technique of known preparation, when carrying out positive pole piece preparation, adds corresponding organic carboxylate in anodal active material and can realize the preparation of the electrochemistry energy memory of different systems as mending the metal additive, and application scope is wide.
The organic carboxylate is used as an additive in the positive electrode plate, and the organic carboxylate does not react with other active materials or inactive materials in the positive electrode plate, and only generates the Kolbe electrolytic decarboxylation reaction when the assembled electrochemical energy storage device is subjected to charge-discharge cycles, and is an irreversible decarboxylation reaction. In addition, based on the active material as the main component of the positive pole piece, the dosage of the positive active material in the positive active material layer is preferably larger than that of the additive, and in order to ensure the charge and discharge capacity of the electrochemical energy storage device, the normal use and the long-term cycling stability of the electrochemical energy storage device, the dosage of the additive is preferably 15-40% of the mass of the positive active material layer.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.

Claims (3)

1. A method of pre-metallization of an electrochemical energy storage device, comprising the steps of:
s1, uniformly mixing the positive electrode active material, the additive, the first binder and the first conductive agent to form positive electrode slurry, coating the positive electrode slurry on the surface of the metal current collector, and drying to obtain a positive electrode;
s2, uniformly mixing the negative electrode active material, the second binder and the second conductive agent to form negative electrode slurry, coating the negative electrode slurry on the surface of the metal current collector, and drying to prepare a negative electrode;
s3, assembling the positive electrode and the negative electrode manufactured in the S1 and the S2, the electrolyte and the diaphragm into an electrochemical energy storage device, performing charge and discharge for at least one cycle under the voltage of 2.0-4.5V, and standing to obtain the electrochemical energy storage device capable of being normally used;
wherein, in step S1, the additive is organic carboxylate with the structure of formula I,
R-(COOM) n (formula I);
the positive active material is active carbon; in step S2, the negative electrode active material is any one of anatase, graphite, porous carbon, or metal oxide; wherein R is H or one of saturated or unsaturated alkyl with 1 or 2 carbon atoms, and M is any one of Li, Na and K; n is 1 to 6 and n is a natural number.
2. The method of pre-metallization of an electrochemical energy storage device according to claim 1, wherein the positive electrode slurry comprises, by mass percent, 40% to 60% of a positive electrode active material, 15% to 40% of an additive, 5% to 15% of a first binder, and 5% to 15% of a first conductive agent.
3. The process of pre-metallization of an electrochemical energy storage device according to claim 2, characterized in that the negative electrode slurry comprises, in mass percent, 70% to 90% of a negative electrode active material, 5% to 15% of a second binder, and 5% to 15% of a second conductive agent.
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