CN113540394A - Positive plate and preparation method thereof, solid-state lithium ion battery, semi-solid-state lithium ion battery and preparation method thereof - Google Patents

Positive plate and preparation method thereof, solid-state lithium ion battery, semi-solid-state lithium ion battery and preparation method thereof Download PDF

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CN113540394A
CN113540394A CN202110812150.2A CN202110812150A CN113540394A CN 113540394 A CN113540394 A CN 113540394A CN 202110812150 A CN202110812150 A CN 202110812150A CN 113540394 A CN113540394 A CN 113540394A
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positive electrode
lithium
lithium ion
solid
ion battery
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CN113540394B (en
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余乐
王仁和
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Vision Power Technology Hubei Co ltd
Envision Power Technology Jiangsu Co Ltd
Envision Ruitai Power Technology Shanghai Co Ltd
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Envision Power Technology Jiangsu Co Ltd
Envision Ruitai Power Technology Shanghai Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0085—Immobilising or gelification of electrolyte
    • 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 application discloses a positive plate and a preparation method thereof, a solid-state lithium ion battery, a semi-solid-state lithium ion battery and a preparation method thereof. The positive electrode sheet includes: the current collector comprises a current collector and a positive slurry layer covering the current collector, wherein a plurality of holes are formed in the positive slurry layer; the positive electrode slurry layer includes a positive electrode active material, a sulfide electrolyte material, and a binder. According to the positive plate, the thick electrode is adopted, the loading capacity of the positive electrode is increased, meanwhile, the porous structure is adopted, the surface area of the positive plate is increased, the lithium ion transmission channel is increased, and the lithium ion transmission performance is improved; the preparation method of the positive plate reduces the cost of the battery; the semisolid lithium ion battery is additionally provided with a lithium ion transmission channel, and the liquid electrolyte is injected, so that good contact between the solid electrolyte and an active substance can be ensured, the lithium ion transmission distance is shortened, the dynamic performance of the battery is improved, and the low-temperature capacity, the normal-rate performance, the normal-temperature cycle life and the high-temperature cycle performance at 45 ℃ of the battery are improved.

Description

Positive plate and preparation method thereof, solid-state lithium ion battery, semi-solid-state lithium ion battery and preparation method thereof
Technical Field
The embodiment of the invention relates to the field of lithium ion batteries, in particular to a positive plate, a preparation method thereof, a solid lithium ion battery, a semi-solid lithium ion battery and a preparation method thereof.
Background
The application range of the lithium ion battery, which is one of the most important electrochemical energy storage devices at present, has gradually expanded from consumer electronics and electric tools to new fields such as new energy electric vehicles, electric ships, electric airplanes and robots. These fields require not only a lithium ion battery with a larger capacity but also a higher demand for its energy density. However, increasing the energy density of the battery tends to result in a reduction in safety performance. Mainstream lithium ion battery in the current market is liquid lithium ion battery, and the oxygen in the positive pole crystal lattice loses the electron easily and takes place oxidation reaction with liquid electrolyte with the form of free oxygen after long-time the use, leads to battery thermal runaway, and in addition, positive negative pole active material reacts with electrolyte easily under the high temperature, leads to the inside short circuit of battery, causes battery thermal runaway. In order to improve the safety of lithium ion batteries, the lithium batteries which are not easy to burn theoretically are developed, and the lithium batteries based on solid electrolytes become the key point of future research.
The existing all-solid-state lithium battery generally has the problem of large volume change during circulation, so that the cohesion of particles in the battery is easily reduced, electrode materials are damaged, and the capacity of the battery is further reduced. In addition, the interfacial problems of the all-solid battery still cannot be solved, such as small solid-solid interface contact area, poor contact, easy separation of the positive plate from the solid electrolyte, slow physical contact, low ionic conductivity, and large interfacial impedance, which in turn leads to reduced coulombic efficiency of the battery. Therefore, it is very critical to develop a solid-state lithium ion battery with large capacity, high conductivity and small solid-solid interface impedance.
Disclosure of Invention
The invention aims to provide a positive plate, a preparation method thereof, a solid-state lithium ion battery, a semi-solid-state lithium ion battery and a preparation method thereof, so that the capacity of the lithium ion battery is higher, the conductivity of the battery is high, and the solid-solid interface impedance is small.
In order to solve the above technical problem, an embodiment of the present invention provides a positive electrode sheet, including: the current collector comprises a current collector and a positive slurry layer covering the current collector, wherein a plurality of holes are formed in the positive slurry layer; the positive electrode slurry layer includes a positive electrode active material, a sulfide electrolyte material, and a binder.
Based on the beneficial effect of improving the energy density of the prepared battery, in some preferable schemes, the thickness of the positive plate is 100-104 μm.
Based on the beneficial effect of improving the energy density of the prepared battery, in some preferable schemes, the load capacity of the positive plate is 28-35 mg/cm2E.g. 32mg/cm2。
In some preferable schemes, the thickness of the positive slurry layer is 80-120 μm; for example 100 μm.
In some preferred embodiments, the positive electrode slurry layer further includes a conductive agent. For example: Super-P.
In some preferred embodiments, the positive electrode slurry layer is obtained by rolling and vacuum-drying a positive electrode slurry.
In some preferred embodiments, the positive electrode slurry includes: the cathode material comprises a cathode active material, a sulfide electrolyte material, a binder and a pore-forming agent.
In some preferred embodiments, the positive electrode slurry further includes a conductive agent.
In some preferred embodiments, the positive electrode slurry includes:
Figure BDA0003168626930000021
the embodiment of the invention also provides a preparation method of the positive plate, which comprises the following steps: and covering the positive slurry layer on a current collector, and rolling and vacuum drying to obtain the positive plate.
In some preferred aspects, in the step of rolling the positive electrode paste layer and the current collector, the rolling is performed on a vertical roll press;
the rolling gap is 60-80 μm, such as 70 μm;
the rolling temperature is 60-80 ℃, for example 70 ℃;
the rolling speed is 5-15 mm/s, such as 10 mm/s.
In some preferred embodiments, the temperature of the vacuum drying is 130 to 170 ℃, more preferably 140 to 160 ℃, for example 150 ℃.
In some preferred embodiments, the positive electrode slurry layer is obtained by stirring and rolling a positive electrode slurry; the positive electrode slurry includes: the cathode material comprises a cathode active material, a sulfide electrolyte material, a binder and a pore-forming agent.
In some preferred aspects, in the step of rolling the positive electrode paste, the rolling is performed on a vertical roll press;
in some preferred embodiments, the rolling gap is gradually decreased from 2000 μm to 60 μm;
in some preferred schemes, the rolling temperature is 60-80 ℃, such as 70 ℃;
in some preferred embodiments, the rolling speed is 5-15 mm/s, such as 10 mm/s;
in some preferred embodiments, the rolling time is not less than 30 minutes, more preferably not less than 40 minutes, more preferably not less than 50 minutes, more preferably not less than 60 minutes; and the rolling time is not more than 110 minutes, more preferably not more than 100 minutes, more preferably not more than 90 minutes, more preferably not more than 80 minutes, for example 60 to 80 minutes.
The embodiment of the invention also provides a semi-solid lithium ion battery, which comprises a positive plate, an electrolyte layer, a negative plate and a liquid electrolyte, wherein the positive plate, the electrolyte layer and the negative plate are sequentially arranged in a contact manner.
In some preferred aspects, the electrolyte layer comprises: the solid sulfide framework layer and the deep eutectic electrolyte layer wrapped on the solid sulfide framework layer;
the solid sulfide framework layer comprises a current collector and a porous sulfide electrolyte layer wrapped on the current collector; the deep eutectic electrolyte layer includes a lithium salt and a poly-nitrogen-containing heteroaromatic compound.
In some preferred schemes, the electrolyte layer is obtained by infiltrating the solid sulfide framework layer with a deep eutectic solution and performing hot pressing treatment; wherein the deep eutectic solution comprises a nitrogen-containing heteroaromatic compound, an initiator and a lithium salt.
In some preferred embodiments, the thickness of the solid sulfide framework layer is 25 to 35 μm, for example 30 μm.
In some preferred embodiments, the porous sulfide electrolyte layer is obtained by treating a sulfide electrolyte material with a pore-forming agent.
In some preferred embodiments, the preparation of the solid sulfide framework layer comprises the steps of: and coating the slurry containing the pore-forming agent and the sulfide electrolyte material on the current collector, rolling and drying in vacuum to obtain the catalyst.
In some preferred embodiments, the pore-forming agent is selenium sulfide (SeS)2) Arsenic sulfide As2S2Lithium sulfide, germanium sulfide, silicon sulfide, for example: and (4) selenium disulfide.
Further, the pore-forming agent is selenium sulfide (SeS) based on the beneficial effects of low reaction temperature required for low boiling point and formation of a compact porous structure2)。
In some preferred aspects, the sulfide electrolyte material is selected from Li2S—GeS2、Li2S—SiS2、(100-x)Li2S—xP2S5(0≤x≤100)、Li2S-MS2-P2S5(M＝Si,Ge,Sn,)、Li2S-MSx-LiX (M ═ P, Si, Ge; X represents a halogen element; X is 0. ltoreq. x.ltoreq.5), thio-LISICON, Li2S-SnS2-P2S5、Li2S-Al2S3-P2S5And Li-Argyrodite, or doping the above systemA modified sulfide electrolyte system.
In some preferred aspects, the sulfide electrolyte material is 80Li2S-20P2S5、75Li2S-25P2S5And related phase, 70Li2S-30P2S5And related phase, Li7P2S8I、Li7P2S8Br0.5I0.5、Li3.25Ge0.25P0.75S4、Li10GeP2S12、Li11Si2PS12、Li9.54Si1.74P1.44S11.7Cl0.3、Li6PS5Cl、Li5.5PS4.5Cl1.5、Li6.6P0.4Ge0.6S5I。
In some preferred embodiments, the current collector is an aluminum foil, a copper foil, a nickel foil, a stainless steel foil, a PI film, a PET film, a PTFE film, for example: aluminum foil.
In some preferred embodiments, the deep eutectic electrolyte layer is obtained by polymerizing a deep eutectic solution, wherein the deep eutectic solution comprises a nitrogen-containing heteroaromatic compound, an initiator and a lithium salt.
In some preferred embodiments, the nitrogen-containing heteroaromatic ring compound is pyridine, at least one hydrogen atom R1-1Substituted pyridines, imidazoles, at least one hydrogen atom being bound by R1-2Substituted imidazoles, pyrroles, having at least one hydrogen atom substituted by R1-3Substituted pyrroles, benzimidazoles, benzopyridines or phenylpropyrroles; wherein, R is1-1、R1-2And R1-3Each independently selected from halogen, C1～4Alkyl, phenyl substituted C1～4Alkyl, phenyl, C1～4Alkyl-substituted phenyl, C1～4Alkoxy radical, C1～4Sulfonyl, C having at least one hydrogen atom substituted by halogen1～4Sulfonyl, pyridyl, C1～4Alkyl substituted pyridyl or thioether groups.
In some preferred embodiments, the nitrogen-containing heteroaromatic ring compound is pyridine, at least one hydrogen atom R1-1Substituted pyridines, imidazoles, at least one hydrogen atom being bound by R1-2Substituted imidazoles or benzimidazoles; wherein R is1-1Is C1～4Alkyl, phenyl substituted C1～4Alkyl, phenyl, C1～4Alkyl-substituted phenyl, C1～4Alkoxy radical, C1～4Sulfonyl, halogen substituted C1～4Sulfonyl, pyridyl or C1～4A mercapto ether group; r1-2At least one hydrogen atom being replaced by C1～4Alkyl radical, C1～4Alkenyl, phenyl substituted C1～4An alkyl substituted imidazole.
In some preferred embodiments, the halogen is fluorine, chlorine, bromine, or iodine;
said C is1～4Alkyl is methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl or tert-butyl;
said C is1～4Alkoxy is methoxy, ethoxy, n-propoxy or n-butoxy;
said C is1～4The sulfonyl is methylsulfonyl, ethylsulfonyl, n-propylsulfonyl, isopropylsulfonyl, n-butylsulfonyl, isobutylsulfonyl, tert-butylsulfonyl;
the pyridyl group is
Figure BDA0003168626930000041
Said C is1～4The sulfide group is
Figure BDA0003168626930000042
Figure BDA0003168626930000043
In some preferred embodiments, the nitrogen-containing heteroaromatic ring compound is selected from any of the following:
Figure BDA0003168626930000044
Figure BDA0003168626930000045
Figure BDA0003168626930000051
the nitrogen-containing heteroaromatic ring compound preferably contains an S atom in the molecular structure thereof, based on the advantageous effect of being more stable in combination with the sulfide electrolyte material, such as:
Figure BDA0003168626930000052
in some preferred embodiments, the lithium salt is selected from lithium hexafluorophosphate (LiPF)6) Lithium tetrafluoroborate (LiBF)4) Lithium perchlorate (LiClO)4) Lithium hexafluoroarsenate (LiAsF)6) Lithium trifluoromethanesulfonate (LiCF)3SO3) Lithium bis (trifluoromethylsulfonyl) imide (LiTFSI), lithium bis (perfluoroethylsulfonyl) imide (LiFSI), (trifluoromethylsulfonyl) (n-perfluorobutylsulfonyl) imide (LiFNTFSI), (fluorosulfonyl) (n-perfluorobutylsulfonyl) imide (LiFNFSI), and lithium bis (oxalato) borate (LiBOB), for example: lithium bis (trifluoromethylsulfonyl) imide.
In some preferred embodiments, the initiator is selected from at least one of Azobisisobutyronitrile (AIBN), Azobisisoheptonitrile (AIVN), dimethyl azobisisobutyrate, hydrogen peroxide, ammonium persulfate, potassium persulfate Benzoyl Peroxide (BPO), benzoyl t-butyl peroxide, and methyl ethyl ketone peroxide.
In some preferred embodiments, the negative electrode is a lithium copper composite tape.
In some preferred aspects, the liquid electrolyte comprises: lithium salts and ionic liquids.
In some preferred embodiments, the ionic liquid is selected from at least one of N-butyl-N-methylpyrrolidine bromide, N-butyl-N-methylpyrrolidine tetrafluoroborate, N-butyl-N-methylpyrrolidine hexafluorophosphate, N-butyl-N-methylpyrrolidine trifluoromethanesulfonate, N-butyl-N-methylpyrrolidine perchlorate, N-butyl-N-methylpyrrolidine bis (trifluoromethanesulfonyl) imide salt.
In some preferred embodiments, in the liquid electrolyte, the lithium salt is selected from at least one of lithium nitrate, lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate, lithium hexafluoroarsenate, lithium trifluoromethanesulfonate, lithium bistrifluoromethylsulfonyl imide, lithium bis (perfluorobutylsulfonyl) imide, lithium (trifluoromethylsulfonyl) (n-perfluorobutylsulfonyl) imide, lithium (fluorosulfonyl) (n-perfluorobutylsulfonyl) imide, or lithium bis (oxalato) borate.
In some preferred embodiments, the concentration of the lithium salt in the liquid electrolyte is 2 mol/l.
Using Pyr14TFSI as a solvent, LiNO3As an electrolyte component of lithium salt, Pyr14TFSI is stable to sulfide electrolyte and lithium metal, LiNO3The film can be formed on the surface of the lithium metal cathode to form an SEI layer related to LiF, LiNxOy-Rich and Li3N-Rich, so that the further reaction of the electrolyte to the lithium metal is delayed;
in some preferred embodiments, the liquid electrolyte contains 2mol of lithium nitrate per liter of the ionic liquid.
In some more preferred embodiments, the ionic liquid is Pyr14TFSI based on the effect of stabilizing the lithium metal anode simultaneously with the sulfide electrolyte material.
LiF, LiNxOy-Rich and Li are formed by film formation on the surface of lithium metal cathode3An SEI layer related to N-Rich for delaying the technical effect of further reaction of the electrolyte on lithium metal, and in some more preferred schemes, the lithium salt is LiNO3。
The embodiment of the invention also provides a preparation method of the semi-solid lithium ion battery, which comprises the following steps: and sequentially attaching the positive electrode, the electrolyte layer and the negative electrode, injecting liquid electrolyte and packaging.
In some preferred embodiments, the preparation of the electrolyte layer comprises the steps of: and coating the deep eutectic solution on the solid sulfide framework layer, and performing hot pressing treatment, wherein the deep eutectic solution comprises a nitrogen-containing heteroaromatic compound, an initiator and a lithium salt.
In order to achieve the effect that the deep eutectic solution fully infiltrates the solid sulfide framework layer and simultaneously prevent the dynamic performance of the electrode from being deteriorated due to the excessively thick loaded electrolyte layer, in some preferred schemes, the distance between the coatings is preferably 7-13 μm, for example 10 μm.
In order to prevent under-or over-polymerization of the deep eutectic solution on the solid sulfide skeleton layer, in some preferred embodiments, the pressure of the hot pressing process is 5 to 10 Mpa.
In order to prevent the deep eutectic solution from under-polymerizing or over-polymerizing on the solid sulfide skeleton layer, in some preferred embodiments, the time of the hot pressing treatment is 80 to 150 minutes, for example, 120 minutes.
In order to enable the deep eutectic solution to be polymerized on the solid sulfide framework layer, in some preferable schemes, the temperature of the hot pressing treatment is 60-90 ℃, for example 75 ℃.
In some preferred embodiments, the step of preparing the sulfide skeleton layer comprises: and coating the slurry containing the pore-forming agent and the sulfide electrolyte material on the current collector, rolling and drying in vacuum to obtain the catalyst.
In some preferred embodiments, the slurry further comprises a carbonate ester, such as dimethyl carbonate.
In some preferable schemes, in the slurry, the mass percentage of the pore-forming agent is 1-50%; more preferably 5-20%; for example: 10 percent.
In some preferable schemes, in the slurry, the mass percentage of the sulfide electrolyte material is 5-20%; for example 90%.
In some preferred embodiments, the slurry has a solid content of 40 to 70%, more preferably 50 to 60%.
In some preferred embodiments, the slurry is obtained by: and dissolving the pore-forming agent and the sulfide electrolyte material in dimethyl carbonate, and stirring to obtain the catalyst.
In some preferred embodiments, the agitation is performed on a Thinky debubbler mixer.
In some preferred embodiments, the stirring time is 5 to 30 minutes, for example 15 minutes.
In some preferable schemes, the rotation speed of the stirring is 200 to 3000 rmp; more preferably 500 to 2000 rmp.
In some preferred schemes, the stirring is divided into a mixing stirring section and a defoaming stirring section.
In some preferred schemes, the rotation speed of the mixing and stirring section is 1000 to 2500rmp, such as 2000rmp, and the stirring time is 6 to 20 minutes, such as 10 minutes; the rotating speed of the defoaming stirring section is 300-700 rmp, such as 500rmp, and the rotating speed is 3-8 minutes, such as 5 minutes.
In some preferred embodiments, the coating gap is 80-120 μm, such as 100 μm.
In some preferred embodiments, the temperature of the drying is 120 to 170 ℃, for example 150 ℃.
In some preferred schemes, the porosity of the sulfide framework layer is 25-35%.
In some preferred embodiments, the molar ratio of the nitrogen-containing heteroaromatic ring compound to the lithium salt in the deep eutectic solution is (1:7) to (7:1), for example 7: 1.
In some preferable schemes, in the deep eutectic solution, the mass percentage of the initiator is 0.1-1%, and more preferably 0.25-0.75%; most preferably 0.4-0.6%; for example 0.5%.
In some preferable schemes, in the deep eutectic solution, the content of the nitrogen-containing heteroaromatic ring compound is 50-97% by mass; more preferably 75-95%; for example: 80 percent.
In some preferred embodiments, the preparing step of the deep eutectic solution comprises: mixing the nitrogen-containing heteroaromatic ring compound and the lithium salt according to the molar ratio of (1:7) - (7:1), and adding an initiator after the solid is completely dissolved to obtain the lithium salt.
In some preferred schemes, the liquid electrolyte is injected into the semi-solid lithium ion battery according to 1 g/Ah.
In some preferred schemes, the liquid electrolyte is injected, then the liquid electrolyte is stood at normal temperature, and then the liquid electrolyte is packaged.
In some preferred embodiments, the standing time at normal temperature is not less than 24 hours, more preferably not less than 36 hours, and still more preferably not less than 48 hours.
Compared with the prior art, the embodiment of the invention has at least the following advantages:
(1) according to the positive plate provided by the embodiment of the invention, the thick electrode is adopted, the loading capacity of the positive electrode is increased, meanwhile, the porous structure is adopted, the surface area of the positive plate is increased, the transmission channel of lithium ions is increased, and the transmission performance of the lithium ions is improved;
(2) according to the preparation method of the positive plate provided by the embodiment of the invention, NMP is not added in the process of homogenizing the positive slurry, so that the environment is protected, the step of recovering a toxic solvent NMP is omitted, and the cost of the battery is reduced;
(3) according to the preparation method of the positive plate provided by the embodiment of the invention, as no liquid solvent is added, the process of solvent vacuum high-temperature drying with huge energy consumption is omitted, and the cost of the battery is reduced;
(4) according to the semi-solid lithium ion battery provided by the embodiment of the invention, the porous positive plate with high load capacity is used, the lithium ion transmission channel is increased, and the liquid electrolyte is injected, so that good contact between the solid electrolyte and an active substance can be ensured, the lithium ion transmission distance is shortened, the dynamic performance of the battery is improved, and the low-temperature capacity, the normal-rate performance, the normal-temperature cycle life and the 45 ℃ high-temperature cycle performance of the battery are improved;
(5) according to the semi-solid lithium ion battery provided by the embodiment of the invention, the porous positive plate is superposed with the porous electrolyte layer, and the liquid electrolyte is injected, so that a lithium ion transmission channel is increased, the interface separation caused by volume expansion and shrinkage in the active material recharging and discharging process is relieved, and the good contact between the positive electrode and the electrolyte layer is ensured, so that the impedance of the finished battery is reduced, and the coulomb efficiency is improved.
As used herein, the term "ionic liquid" refers to an ionic compound consisting entirely of anions and cations and being in a liquid state at 20-30 ℃.
It is to be understood that within the scope of the present invention, the above-described features of the present invention and those specifically described below (e.g., in the examples) may be combined with each other to form new or preferred embodiments. Not to be reiterated herein, but to the extent of space.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the present invention is further described below with reference to specific embodiments. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The experimental procedures, in which specific conditions are not noted in the following examples, are generally carried out under conventional conditions or conditions recommended by the manufacturers. Unless otherwise indicated, percentages and parts are percentages and parts by weight. The test materials and reagents used in the following examples are commercially available without specific reference.
Unless otherwise defined, technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs, and it is to be noted that the terms used herein are merely for describing particular embodiments and are not intended to limit example embodiments of the present application.
Example 1 preparation of Positive electrode sheet
The preparation process of the positive plate is completely finished under the dew point condition of-70 ℃, and selenium disulfide, lithium nitrate and materials are firstly dewatered before experimental operation, so that the water content of the materials is ensured to be less than or equal to 10 ppm.
Mixing NCM622 material and Li6PS5Cl, PTFE powder, Super-P and selenium disulfide are mixed, wherein the mass fraction of the NCM622 material is 70 percent, and Li is6PS5The mass fraction of Cl is 23%, the mass fraction of PTFE powder is 3%, the mass fraction of Super-P is 2% and the mass fraction of selenium disulfide is 2%. Stirring for 2min by using a Waring 800s high-speed triturator, resting for 1min, and repeatedly operating for 15-20 times to obtain the anode slurry.
Repeatedly rolling the obtained positive electrode slurry by using a vertical roller press, gradually decreasing the rolling gap from 2000 micrometers to 60 micrometers, the rolling temperature is 70 ℃, and the rolling speed is 10mm/s until the positive electrode slurry is rolled into a uniform sheet shape with the thickness of 100 DEGAbout μm, and rolling for about 60-80 min. After the rolling is finished, the obtained sheet and the aluminum foil are rolled and compounded into the aluminum foil with the thickness of 12 mu m, the rolling gap of 70 mu m, the rolling temperature of 70 ℃, the rolling speed of 10mm/s, the sheet and the aluminum foil are rolled to the thickness of about 100-104 mu m on a single side and the Loading of 32mg/cm2About, vacuum drying at 150 deg.C, during which SeS2Completely volatilizing, and observing a three-dimensional structure with a uniform pore structure in the pole piece by an electron microscope to obtain the positive pole piece; the weight was 16.7mg, calculated to be 35% porosity of the positive plate.
Example 2 preparation of electrolyte layer
The preparation process is completely carried out in an argon environment glove box with water less than or equal to 0.1ppm, oxygen less than or equal to 0.1ppm and carbon dioxide less than or equal to 0.1ppm, the 2,2' -dipyridyl disulfide and LiTFSI materials are firstly dewatered before experimental operation, and the water content of the materials is ensured to be less than or equal to 10 ppm;
(1) preparation of sulfide framework layer
90 percent of lithium phosphorus sulfur chloride (Li) by mass fraction6PS5Cl) electrolyte material and selenium disulfide with the mass fraction of 10 percent are mixed, dimethyl carbonate is taken as a solvent, the solid content is about 50-60 percent, a Thinky defoaming stirrer is used for stirring for 10 minutes at 2000rmp, and then defoaming stirring is carried out for 5 minutes at 500 rmp;
and uniformly coating the mixed sulfide electrolyte slurry on an aluminum foil, wherein the coating gap is 100 microns, and the coated material is dried in vacuum at room temperature to obtain the sulfide framework layer. Rolling the obtained sulfide framework layer until the thickness is 30 mu m, and then drying the sulfide framework layer at 150 ℃ in vacuum, wherein selenium disulfide is completely volatilized in the process, and the interior of the sulfide framework layer is observed to form a three-dimensional structure with a uniform pore structure by an electron microscope; the weight was 5mg, calculated as 30% porosity of the sulfide framework layer.
(2) Preparation of deep eutectic solution
Preparing 2,2' -dipyridyl disulfide with a molar fraction of 80% and lithium bis (trifluoromethylsulfonyl) imide with a molar fraction of 20%, and adding azobisisobutyronitrile with a mass fraction of 0.5% to mix into a solution after solid materials are completely dissolved and reach room temperature, so as to obtain a deep eutectic solution. And placing the obtained deep eutectic solution in a refrigerator at the temperature of 2-6 ℃ for later use.
(3) Preparation of composite electrolyte layer
Coating the deep eutectic solution prepared in the step (2) on the sulfide framework layers, wherein the coating gap is 10 mu m, and after the deep eutectic solution completely infiltrates the sulfide framework layers, placing the deep eutectic solution into an aluminum plastic film for sealing; and taking the sealed aluminum-plastic layer out of the glove box to carry out flat plate hot pressing treatment, wherein the flat plate hot pressing pressure is 5-10Mpa, the time is 120 minutes, the temperature is 75 ℃, and after the hot pressing treatment is finished, taking the aluminum-plastic layer out of the flat plate hot pressing machine to obtain the composite electrolyte layer.
Example 3 preparation of semi-solid lithium ion batteries
Configuration of liquid electrolyte:
lithium nitrate was dissolved in PyR14TFSI ionic liquid to prepare a 2mol/L lithium nitrate solution.
Assembling the lithium ion battery:
the positive plate prepared in example 1, the electrolyte layer prepared in example 2 and a lithium metal negative plate (lithium copper composite strip, lithium foil thickness 50 μm, copper foil thickness 10 μm) were subjected to tab welding on the positive plate and the negative plate, a nickel copper tab was welded on the negative plate, an aluminum tab was welded on the positive plate, the upper part was then encapsulated with a side encapsulation machine, the prepared liquid electrolyte was injected into the remaining side, the liquid electrolyte was added to the battery at a ratio of 1g/Ah, after the injection, the battery was allowed to stand at room temperature for 48 hours, and finally the battery was sealed with an encapsulation machine to obtain a semi-solid lithium ion battery.
Example 4 preparation of semi-solid lithium ion batteries
The method for preparing a semi-solid lithium ion battery in example 4 is substantially the same as in example 3, except that the electrolyte layer used is a non-porous electrolyte layer, and the preparation process is as follows:
the preparation process is completely carried out in an argon environment glove box with water less than or equal to 0.1ppm, oxygen less than or equal to 0.1ppm and carbon dioxide less than or equal to 0.1ppm, and before experimental operation, the water content of the material is firstly ensured to be less than or equal to 10 ppm;
97 percent of lithium phosphorus sulfur chloride (Li) by mass fraction6PS5Cl) electrolyte material, 3 percent of PVdF by mass, butyl butyrate as solvent, and solid content of about 50 to E60%, stirring the resulting mixture at 2000rmp for 10 minutes by using a Thinky defoaming stirrer, and then defoaming and stirring the resulting mixture at 500rmp for 5 minutes;
and uniformly coating the mixed sulfide electrolyte slurry on an aluminum foil, wherein the coating gap is 100 microns, the coated material is dried in vacuum at 110 ℃, and the obtained sulfide electrolyte layer is rolled to the thickness of 30 microns to obtain the non-porous sulfide electrolyte layer.
Example 5 preparation of semi-solid lithium ion batteries
The method for preparing a semi-solid lithium ion battery in example 5 was substantially the same as in example 3, except that the liquid electrolyte used was PyR14FSI ionic liquid, configured as a 2mol/L LiFSI solution.
Comparative example 1
(1) Preparing a positive plate:
the preparation process of the positive plate is completely finished under the dew point condition of-70 ℃, and the material needs to be dewatered before experimental operation, so that the water content of the material is ensured to be less than or equal to 10 ppm.
Mixing NCM622 material and Li6PS5Cl, PTFE powder and Super-P, wherein the mass fraction of the NCM622 material is 70 percent, and Li is6PS5The mass fraction of Cl is 25%, the mass fraction of PTFE powder is 3%, and the mass fraction of Super-P is 2%. Stirring for 2min by using a Waring 800s high-speed triturator, resting for 1min, and repeatedly operating for 15-20 times to obtain the anode slurry.
Repeatedly rolling the obtained anode slurry by using a vertical roller press, gradually decreasing the rolling gap from 2000 micrometers to 60 micrometers, wherein the rolling temperature is 70 ℃, the rolling speed is 10mm/s until the anode slurry is rolled to be uniform sheet-shaped, the thickness is about 100 micrometers, and the rolling time is about 60-80 min. After the rolling is finished, the obtained sheet and the aluminum foil are rolled and compounded into the aluminum foil with the thickness of 12 mu m, the rolling gap of 70 mu m, the rolling temperature of 70 ℃, the rolling speed of 10mm/s, the sheet and the aluminum foil are rolled to the thickness of about 100-104 mu m on a single side and the Loading of 32mg/cm2And (4) controlling to obtain the positive plate.
(2) Preparation of all-solid-state lithium ion battery
The positive electrode sheet prepared in the step (1), the non-porous electrolyte prepared in example 4, and lithium metal were assembled using a lamination method to prepare an all-solid-state lithium ion battery.
Comparative example 2
The positive electrode sheet prepared in comparative example 1, the non-porous electrolyte prepared in example 4, and lithium metal were assembled using a lamination method, and a commercially available electrolyte (EC: EMC: DMC V: 1:1:1, LiPF 61 mol/L VC 1%) was injected at 1g/Ah to prepare a semi-solid lithium ion battery.
Comparative example 3
The positive electrode sheet prepared in comparative example 1, the composite electrolyte layer prepared in example 1, and lithium metal were assembled using a lamination method to prepare an all-solid lithium ion battery.
Comparative example 4
The positive electrode sheet prepared in comparative example 1, the composite electrolyte layer prepared in example 1, and lithium metal were assembled using a lamination method, and a commercially available electrolyte (EC: EMC: DMC V: 1:1:1, LiPF 61 mol/L VC 1%) was injected at 1g/Ah to prepare a semi-solid lithium ion battery.
Test example 1 ordinary temperature cycle life test
The capacity retention rate was measured in 200 cycles at normal temperature as shown in table 1 below, and the results are reported in table 5.
TABLE 1
Figure BDA0003168626930000111
Figure BDA0003168626930000121
Test example 2 Low temperature Capacity Retention test
The low temperature capacity retention rate was measured at-20 ℃ in the steps shown in table 2 below, and the low temperature capacity retention rate was ═ low temperature capacity/normal temperature capacity × 100%, and the results are reported in table 5.
TABLE 2
Number of steps Working steps Mode of operation Ambient temperature Interval of sampling point
1 Standing still Rest 5min； 25℃ 30s
2 Constant current and constant voltage charging 1/3C CC to 4.2V，CV to 0.05C； 25℃ 5s
3 Standing still Rest 5min； 25℃ 30s
4 Constant current discharge 1/3C DC to 2.5V； 25℃ 5s
5 Standing still Rest 5min； 25℃ 30s
6 Standing still Rest 5min； 25℃ 30s
7 Constant current and constant voltage charging 1/3C CC to 4.2V，CV to 0.05C； 25℃ 5s
8 Standing still Rest 60min； -20℃ 30s
9 Constant current discharge 1/3C DC to 2.5V； -20℃ 5s
10 Standing still Rest 5min； -20℃ 30s
Test example 3 test of room temperature Rate Performance
The room temperature rate performance was tested in the steps shown in table 3 below, and the rate performance of the battery was 2C capacity/0.33C capacity × 100%.
TABLE 3
Figure BDA0003168626930000122
Figure BDA0003168626930000131
Test example 4 DC internal resistance test
The DCR test method using 50% SOC was tested in the steps described in table 4 below.
TABLE 4
Figure BDA0003168626930000132
Figure BDA0003168626930000141
The direct current internal resistance R of the battery is delta V/I, the direct current internal resistance obtained in the example 3 is recorded as R1, the direct current internal resistance obtained in the comparative example 3 is recorded as R2, the direct current internal resistance obtained in the comparative example 4 is recorded as R3, the direct current internal resistance obtained by the common all-solid-state lithium ion battery is recorded as R4, and other DCR ratios obtained by R2/R1, R3/R1 and R4/R1 are calculated by taking R1/R1 as 100 percent; record to table 5.
TABLE 5
Figure BDA0003168626930000142
Test example 5 safety Performance test
And (3) needle punching test:
referring to GBT31485-2015 power storage battery safety requirements and test methods for electric automobiles,
the method comprises the following steps:
a) charging the single battery;
b) by using
Figure BDA0003168626930000143
The high temperature resistant steel needle (the conical angle of the needle tip is 45 degrees, the surface of the needle is smooth and clean and has no rust, oxide layer and oil stain) penetrates through the battery plate from the direction vertical to the battery plate at the speed of 25mm/s, the penetrating position is close to the geometric center of the punctured surface, and the steel needle stays in the battery;
c) observe for 1 h.
TABLE 6
Group of Phenomenon(s)
Example 3 No smoking and fire
Example 4 No smoking and fire
Example 5 Smoking without causing fire
Commercially available liquid lithium ion battery On fire
Market-sold semi-solid lithium ion battery On fire
It will be understood by those of ordinary skill in the art that the foregoing embodiments are specific examples for carrying out the invention, and that various changes in form and details may be made therein without departing from the spirit and scope of the invention in practice.

Claims (29)

1. A positive electrode sheet, comprising: the current collector comprises a current collector and a positive slurry layer covering the current collector, wherein a plurality of holes are formed in the positive slurry layer, and the positive slurry layer comprises a positive active material, a sulfide electrolyte material and a binder.
2. The positive electrode sheet according to claim 1, wherein the thickness of the positive electrode sheet is 100 to 104 μm.
3. The positive electrode sheet according to claim 1, wherein the positive electrode sheet has a load of 28 to 35mg/cm2。
4. The positive electrode sheet according to claim 1, wherein the positive electrode slurry layer further comprises a conductive agent.
5. The positive electrode sheet according to claim 1, wherein the positive electrode slurry layer is obtained by subjecting a positive electrode slurry to rolling and vacuum drying.
6. The positive electrode sheet according to claim 5, wherein the positive electrode slurry comprises: the cathode material comprises a cathode active material, a sulfide electrolyte material, a binder and a pore-forming agent.
7. The positive electrode sheet according to claim 6, wherein the positive electrode slurry further comprises a conductive agent.
8. The positive electrode sheet according to claim 5, wherein the positive electrode slurry comprises:
55-75% of a positive electrode active material;
20-25% of sulfide electrolyte material;
1-5% of a binder;
1-5% of pore-forming agent;
1-5% of a conductive agent.
9. A method for preparing a positive plate is characterized by comprising the following steps: and covering the positive slurry layer on a current collector, and rolling and vacuum drying to obtain the positive plate.
10. The production method according to claim 9, wherein in the step of rolling the positive electrode paste layer and the current collector, the rolling is performed on a vertical roll press;
and/or the rolling gap is 60-80 μm;
and/or the rolling temperature is 60-80 ℃;
and/or the rolling speed is 5-15 mm/s;
and/or the temperature of the vacuum drying is 130-170 ℃.
11. The production method according to claim 9, characterized in that the positive electrode slurry layer is obtained by stirring and rolling a positive electrode slurry; the positive electrode slurry includes: the cathode material comprises a cathode active material, a sulfide electrolyte material, a binder and a pore-forming agent.
12. The production method according to claim 11, wherein in the step of rolling the positive electrode paste, the rolling is performed on a vertical roll press;
and/or, the rolling gap is gradually decreased from 2000 μm to 60 μm;
and/or the rolling temperature is 60-80 ℃;
and/or the rolling speed is 5-15 mm/s;
and/or the rolling time is not less than 30 minutes, and the rolling time is not more than 110 minutes.
13. A solid-state lithium ion battery, characterized in that the lithium ion battery comprises the positive electrode sheet according to any one of claims 1 to 8.
14. A semi-solid lithium ion battery, characterized in that it comprises a positive electrode sheet, an electrolyte layer and a negative electrode sheet according to any one of claims 1 to 8, and a liquid electrolyte, in sequential contact arrangement.
15. The semi-solid lithium ion battery of claim 14, wherein the electrolyte layer comprises: the solid sulfide framework layer and the deep eutectic electrolyte layer wrapped on the solid sulfide framework layer;
the solid sulfide framework layer comprises a current collector and a porous sulfide electrolyte layer wrapped on the current collector; the deep eutectic electrolyte layer includes a lithium salt and a poly-nitrogen-containing heteroaromatic compound.
16. The semi-solid lithium ion battery of claim 15, wherein the electrolyte layer is obtained by infiltrating the solid sulfide skeleton layer with a deep eutectic solution and performing a hot pressing process; wherein the deep eutectic solution comprises a nitrogen-containing heteroaromatic compound, an initiator and a lithium salt.
17. The semi-solid lithium ion battery of claim 15, wherein the porous sulfide electrolyte layer is obtained by treating a sulfide electrolyte material with a pore former.
18. The semi-solid lithium ion battery of claim 15, wherein the sulfide electrolyte material is selected from Li2S—GeS2、Li2S—SiS2、(100-x)Li2S—xP2S5(0≤x≤100)、Li2S-MS2-P2S5(M＝Si,Ge,Sn,)、Li2S-MSx-LiX (M ═ P, Si, Ge; X represents a halogen element; 0. ltoreq. X≤5)、thio-LISICON、Li2S-SnS2-P2S5、Li2S-Al2S3-P2S5And Li-Argyrodite.
19. The semi-solid lithium ion battery of claim 15, wherein the deep eutectic electrolyte layer is obtained by polymerization of a deep eutectic solution comprising a nitrogen-containing heteroaromatic ring compound, an initiator, and a lithium salt.
20. The semi-solid lithium ion battery of claim 19, wherein the nitrogen-containing heteroaromatic ring compound is pyridine, at least one hydrogen atom R1-1Substituted pyridines, imidazoles, at least one hydrogen atom being bound by R1-2Substituted imidazoles, pyrroles, having at least one hydrogen atom substituted by R1-3Substituted pyrroles, benzimidazoles, benzopyridines or phenylpropyrroles; wherein, R is1-1、R1-2And R1-3Each independently selected from halogen, C1～4Alkyl, phenyl substituted C1～4Alkyl, phenyl, C1～4Alkyl-substituted phenyl, C1～4Alkoxy radical, C1～4Sulfonyl, C having at least one hydrogen atom substituted by halogen1～4Sulfonyl, pyridyl, C1～4Alkyl substituted pyridyl or thioether groups.
21. The semi-solid lithium ion battery of claim 19, wherein the nitrogen-containing heteroaromatic ring compound is selected from any one of:
Figure FDA0003168626920000031
Figure FDA0003168626920000032
22. the semi-solid lithium ion battery of claim 19, wherein the lithium salt is selected from the group consisting of hexafluorophosphorsLithium carbonate (LiPF)6) Lithium tetrafluoroborate (LiBF)4) Lithium perchlorate (LiClO)4) Lithium hexafluoroarsenate (LiAsF)6) Lithium trifluoromethanesulfonate (LiCF)3SO3) At least one of lithium bis (trifluoromethylsulfonyl) imide (LiTFSI), lithium bis (perfluoroethylsulfonyl) imide (LiFSI), (trifluoromethylsulfonyl) (n-perfluorobutylsulfonyl) imide (LiFNTFSI), (fluorosulfonyl) (n-perfluorobutylsulfonyl) imide (LiFNFSI), and lithium bis (oxalato) borate (LiBOB);
and/or the initiator is selected from at least one of Azobisisobutyronitrile (AIBN), Azobisisoheptonitrile (AIVN), dimethyl azobisisobutyrate, hydrogen peroxide, ammonium persulfate, potassium persulfate Benzoyl Peroxide (BPO), benzoyl peroxide tert-butyl ester and methyl ethyl ketone peroxide.
23. The semi-solid lithium ion battery of claim 14, wherein the liquid electrolyte comprises: lithium salts and ionic liquids.
24. The semi-solid lithium ion battery of claim 23, wherein the ionic liquid is selected from at least one of N-butyl-N-methylpyrrolidine bromide, N-butyl-N-methylpyrrolidine tetrafluoroborate, N-butyl-N-methylpyrrolidine hexafluorophosphate, N-butyl-N-methylpyrrolidine trifluoromethanesulfonate, N-butyl-N-methylpyrrolidine perchlorate, N-butyl-N-methylpyrrolidine bis (trifluoromethanesulfonyl) imide salt;
and/or, in the liquid electrolyte, the lithium salt is selected from at least one of lithium nitrate, lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate, lithium hexafluoroarsenate, lithium trifluoromethanesulfonate, lithium bistrifluoromethylsulfonyl imide, lithium bis (perfluorobutylsulfonyl) imide, lithium (trifluoromethylsulfonyl) (n-perfluorobutylsulfonyl) imide, lithium (fluorosulfonyl) (n-perfluorobutylsulfonyl) imide or lithium bis (oxalato) borate.
25. The semi-solid lithium ion battery of claim 23, wherein the liquid electrolyte contains 2mol lithium nitrate per liter ionic liquid.
26. A method for preparing a semi-solid lithium ion battery, the method comprising the steps of: attaching a positive electrode, an electrolyte layer and a negative electrode in this order, injecting a liquid electrolyte and packaging, wherein the positive electrode is obtained by the production method according to any one of claims 9 to 12.
27. The production method according to claim 26, wherein the production of the electrolyte layer comprises the steps of: and coating a deep eutectic solution on the solid sulfide framework layer, and performing hot pressing treatment, wherein the deep eutectic solution comprises a nitrogen-containing heteroaromatic compound, an initiator and a lithium salt.
28. The method of claim 26, wherein the liquid electrolyte is injected into the semi-solid lithium ion battery at 1 g/Ah.
29. The method according to claim 26, wherein the liquid electrolyte is injected, then left at room temperature, and then packaged.
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