CN117039180A - In-situ polymerization semi-solid battery and preparation method thereof - Google Patents
In-situ polymerization semi-solid battery and preparation method thereof Download PDFInfo
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- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 38
- 239000007787 solid Substances 0.000 title claims abstract description 29
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000003792 electrolyte Substances 0.000 claims abstract description 71
- 239000000178 monomer Substances 0.000 claims abstract description 59
- 238000002347 injection Methods 0.000 claims abstract description 38
- 239000007924 injection Substances 0.000 claims abstract description 38
- 239000003999 initiator Substances 0.000 claims abstract description 36
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- IBVPVTPPYGGAEL-UHFFFAOYSA-N 1,3-bis(prop-1-en-2-yl)benzene Chemical compound CC(=C)C1=CC=CC(C(C)=C)=C1 IBVPVTPPYGGAEL-UHFFFAOYSA-N 0.000 claims description 4
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- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052744 lithium Inorganic materials 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
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- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 3
- FRMOHNDAXZZWQI-UHFFFAOYSA-N lithium manganese(2+) nickel(2+) oxygen(2-) Chemical compound [O-2].[Mn+2].[Ni+2].[Li+] FRMOHNDAXZZWQI-UHFFFAOYSA-N 0.000 claims description 3
- DVATZODUVBMYHN-UHFFFAOYSA-K lithium;iron(2+);manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[Fe+2].[O-]P([O-])([O-])=O DVATZODUVBMYHN-UHFFFAOYSA-K 0.000 claims description 3
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 3
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- QTKPMCIBUROOGY-UHFFFAOYSA-N 2,2,2-trifluoroethyl 2-methylprop-2-enoate Chemical group CC(=C)C(=O)OCC(F)(F)F QTKPMCIBUROOGY-UHFFFAOYSA-N 0.000 description 1
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- 229910015872 LiNi0.8Co0.1Mn0.1O2 Inorganic materials 0.000 description 1
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Classifications
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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
- H01M10/058—Construction or manufacture
-
- 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
-
- 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
- H01M2300/00—Electrolytes
- H01M2300/0085—Immobilising or gelification of electrolyte
-
- 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
- H01M2300/0088—Composites
- H01M2300/0091—Composites in the form of mixtures
Abstract
The invention discloses an in-situ polymerization semi-solid battery and a preparation method thereof, wherein the preparation method comprises the following steps: s1, assembling a dry cell; s2, primary liquid injection: injecting a mixed solution into the dry cell, wherein the mixed solution comprises a monomer, a first initiator and a solvent, and the monomer contains at least two asymmetric double bonds; s3, carrying out high-temperature prepolymerization to enable at least one double bond of the monomer to carry out prepolymerization reaction under the initiation of a first initiator so as to form a prepolymer; s4, drying at a high temperature to volatilize and discharge the residual solvent and the monomer which does not undergo the prepolymerization reaction at a high temperature; s5, secondary liquid injection: injecting part of electrolyte into the dry cell; s6, standing uniformly, forming and aging; s7, three liquid injection: injecting a second initiator and the rest electrolyte into the dry cell; and S8, aging and polymerizing at high temperature to form a gel polymer, thus obtaining the semi-solid battery. The invention can effectively solve the problems of overhigh content of residual monomer of the semi-solid battery and poor wettability.
Description
Technical Field
The invention relates to the technical field of semi-solid battery production, in particular to an in-situ polymerization semi-solid battery and a preparation method thereof.
Background
With the gradual increase of the demand of the power battery, great challenges are presented to the endurance mileage and the safety performance of the battery. In the traditional lithium ion power battery, the positive electrode material mainly comprises two major types of lithium iron phosphate and ternary materials, wherein the lithium iron phosphate has good safety due to high self-decomposition temperature, but the lithium iron phosphate is difficult to meet the requirements on endurance mileage due to low-temperature performance, low energy density and the like, and particularly has more prominent disadvantages in the northern low-temperature environment. The ternary battery has good performance in a low-temperature environment and high energy density, and can meet the requirements of consumers on the endurance mileage especially after carrying the cathode material with high specific energy, but the ternary material has relatively strong activity, relatively poor thermal stability and seriously affects the safety performance of the battery.
Based on the above, the concept of replacing the traditional electrolyte with the solid electrolyte is proposed in the industry, the solid electrolyte is high in rigidity, the growth of lithium dendrite can be restrained, the electrochemical window is wider, the energy density of the battery can be improved, the leakage can be effectively prevented, and the safety performance of the battery is improved. However, in practical application, the electrochemical performance of the battery is difficult to improve due to poor contact between the solid electrolyte and the interface.
The in-situ polymerization semi-solid battery is mainly formed by in-situ solidification, monomer is dissolved in electrolyte, and is injected into the battery core in a liquid injection mode, and after the electrolyte is fully soaked, the monomer is initiated to polymerize under a certain condition to form the semi-solid battery. The in-situ polymerization semi-solid battery can effectively reduce the use amount of electrolyte in the battery, improve the contact interface between the positive and negative electrode plates and the electrolyte, and can tightly adhere the diaphragm to the surface of the electrode plate due to the adhesive property of gel, thereby improving the heat shrinkage performance of the diaphragm and improving the safety performance of the battery. However, the existing synthesis method of the in-situ polymerization semi-solid battery is unreasonable in design, so that the residual monomer amount in the later period is too high, the anode-cathode interface film is affected, the electrolyte infiltration effect is poor, the consistency of the battery is poor, and the capacity of the battery is not easy to develop.
Disclosure of Invention
In order to overcome the defects, the invention aims to provide an in-situ polymerization semi-solid battery and a preparation method thereof, which can effectively solve the problems of overhigh content of residual monomer and poor wettability of the semi-solid battery.
In order to achieve the above purpose, one of the technical schemes adopted by the invention is as follows: the preparation method of the in-situ polymerization semi-solid battery comprises the following steps:
s1, assembling a dry cell;
s2, primary liquid injection: injecting a mixed solution into the dry cell, wherein the mixed solution comprises a monomer, a first initiator and a solvent, and the monomer contains at least two asymmetric double bonds;
s3, carrying out high-temperature prepolymerization to enable at least one double bond of the monomer to carry out prepolymerization reaction under the initiation of a first initiator so as to form a prepolymer;
s4, drying at a high temperature to volatilize and discharge the residual solvent and the monomer which does not undergo the prepolymerization reaction at a high temperature;
s5, secondary liquid injection: injecting part of electrolyte into the dry cell;
s6, standing uniformly, forming and aging;
s7, three liquid injection: injecting a second initiator and the rest electrolyte into the dry cell;
and S8, aging and polymerizing at high temperature to form a gel polymer, thus obtaining the semi-solid battery.
The preparation method of the invention has the beneficial effects that:
in the step S2, when the liquid is injected once, as the injected monomer contains at least two asymmetric double bonds, the difference of the activity intensity of different double bonds exists, so that the polymerization degree and the polymerization time of different double bonds can be controlled through different initiation conditions, and the polymerization sequence of different double bonds can be controlled conveniently; then, in the high-temperature prepolymerization in the step S3, firstly initiating a relatively active double bond through an initiator to polymerize so as to form a prepolymer; removing the residual solvent and the monomer which do not participate in the reaction after the pre-polymerization reaction through the step S4 so as to reduce the residual quantity of the monomer in the later stage; then aging (small-rate charging) is carried out after part of electrolyte is injected in the steps S5 and S6, so that a solvation structure can be formed between the prepolymer and lithium ions in the electrolyte, the uniformity of the concentration of the prepolymer in the electrolyte and the wettability of the prepolymer in the electrode plate are improved through the movement of the lithium ions, and the consistency of the subsequent internal solution is further ensured; and through formation and aging after secondary liquid injection, the uniform mixing of the electrolyte and the prepolymer can be ensured, and the phenomenon that the prepolymer in the gap between the positive electrode and the negative electrode prevents the electrolyte from being immersed can be avoided; and finally, carrying out three-time liquid injection, aging and high-temperature polymerization through the step S7 and the step S8 so as to polymerize the less active double bonds in the monomer to form a gel network, closely attaching positive and negative interfaces, further improving the interface contact of the electrolyte and improving the electrochemical performance of the battery.
In the invention, the monomer is polymerized in two steps, the first step is to polymerize the more active double bond in the monomer firstly through the high temperature pre-polymerization in the step S3, and the second step is to polymerize the less active double bond in the monomer through the high temperature polymerization in the step S8, so that the monomer finally forms a gel network capable of bonding the anode-cathode interface; the arrangement of step polymerization can pre-form prepolymer before injecting electrolyte, so as to be beneficial to the infiltration effect of the prepolymer between positive and negative electrode particles and further beneficial to the consistency of the battery.
The semi-solid battery formed by the in-situ polymerization of the primary injection is poor in later electrochemical performance due to high monomer residual quantity, so that the invention adopts the tertiary injection, the volatile solvent is injected during the primary injection, unreacted monomers and residual solvent are removed by high-temperature drying after the high-temperature pre-polymerization, and then the secondary injection is subjected to formation charging, thereby being beneficial to uniform mixing of the pre-polymer and the electrolyte and improving wettability, and further ensuring the consistency of internal solution after the tertiary injection.
Further, in step S2, the monomer includes at least one of 1, 3-diisopropenylbenzene, 1, 3-hexadiene, 1, 4-poly (4, 8-2-methyl-1, 3, 7-nonyltriene), 1-hydroxydicyclopentadiene, 5-isopropyl-2-methylcyclohexa-1, 3-diene, allene phosphonic acid, 1-methoxy-3-trimethylsiloxy-1, 3-butadiene, 3-methylene-7-methyl-1, 6-octadiene.
Further, in step S2, the first initiator includes at least one of azobisisobutyronitrile, dibenzoyl peroxide, azobisisoheptonitrile, 2-azobisisobutyronitrile.
Further, in step S2, the solvent includes at least one of dimethyl carbonate, diethyl carbonate, methylethyl carbonate, ethylene carbonate, propylene carbonate.
Further, in the mixed solution, the weight ratio of the monomer is 2-40 wt%, the weight ratio of the first initiator is 0.05-1 wt%, and the weight ratio of the solvent is 59-97 wt%.
Further, in step S3, the high temperature prepolymerization is carried out at a temperature of 35 to 100℃for a period of 1 to 48 hours. Illustratively, the high temperature prepolymerization temperature is 45 ℃, 65 ℃, 85 ℃ and the like, and the prepolymerization time is 24 hours, 48 hours and the like.
Further, in step S4, the high temperature drying is performed at 60 to 100 ℃ for 24 to 72 hours. Illustratively, the high temperature drying temperature is 60 ℃, 72 ℃, 85 ℃ and the like, and the drying time is 24 hours, 36 hours, 48 hours, 60 hours, 72 hours and the like.
Residual monomers and solvents are dried after high-temperature prepolymerization, so that the reactivity of the later monomers at the interfaces of the anode and the cathode can be reduced, and the in-situ prepolymerization of the monomers is beneficial to the infiltration effect of the prepolymer between the anode and the cathode particles, and the adhesive effect of the monomers can be used as an artificial interfacial film, so that the electrochemical performance and the safety performance of the battery are improved.
Further, the electrolyte of the secondary injection accounts for 70-95 wt% of the total electrolyte, and the electrolyte of the tertiary injection accounts for 5-30 wt% of the total electrolyte.
Further, the second initiator includes at least one of azobisisobutyronitrile, dibenzoyl peroxide, azobisisoheptonitrile, 2-azobisisobutyronitrile, and the second initiator is different from the first initiator. Different double bonds can be initiated to react by the selection of different initiators.
Further, in step S8, the high-temperature polymerization is performed at a temperature of 60 to 100℃for 24 to 72 hours. Illustratively, the high temperature polymerization temperature is 60 ℃, 65 ℃, 85 ℃ and the like, and the high temperature polymerization time is 24 hours, 36 hours, 48 hours, 72 hours and the like.
Further, step S1 includes: and respectively preparing a positive plate, a negative plate and a diaphragm, and then assembling the positive plate, the negative plate and the diaphragm into a shell to prepare the dry battery cell.
Further, the positive electrode sheet comprises at least one of Lithium Nickel Manganese Oxide (LNMO), lithium iron manganese phosphate or ternary materials (such as NCM11, NCM532, NCM622, NCM712, NCM811, NCA); the negative electrode sheet comprises at least one of graphite, silicon-doped graphite or lithium metal negative electrode, wherein the silicon content in the silicon-doped graphite is 2-40 wt%.
The second technical scheme adopted by the invention is as follows: an in-situ polymerized semi-solid battery is prepared by adopting any one of the preparation methods. The in-situ polymerization semi-solid battery can effectively reduce monomer residual quantity, improve the wettability of electrolyte, reduce the risk of leakage, and improve the interface contact of the electrolyte, thereby improving the cycle performance and the safety performance of the battery.
Detailed Description
The following detailed description of the preferred embodiments of the invention is provided to enable those skilled in the art to more readily understand the advantages and features of the invention and to make a clear and concise definition of the scope of the invention. It should be noted that the following examples are provided for better understanding of the present invention, and are not limited to the preferred embodiments, but are not limited to the content and the protection scope of the present invention, and any product which is the same as or similar to the present invention and obtained by combining the present invention with other features of the prior art in the light of the present invention falls within the protection scope of the present invention.
It should be noted that in the description of the present specification, descriptions of terms "one embodiment," "some embodiments," "illustrative embodiments," "examples," "specific examples," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiments or examples. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
Furthermore, the examples do not address specific experimental procedures or conditions, and may be performed according to the procedures or conditions of conventional experimental procedures described in the literature in this field. In the examples, the numerical ranges shown using "to" represent ranges including the numerical values described before and after "to" as the minimum value and the maximum value, respectively. The reagents or apparatus used were conventional reagent products commercially available without the manufacturer's knowledge.
Examples
The invention discloses a preparation method of an in-situ polymerization semi-solid battery, which comprises the following steps:
s1, assembling a dry cell: preparing a positive plate, a negative plate and a diaphragm respectively, and then assembling the positive plate, the negative plate and the diaphragm into a shell to prepare a dry cell, wherein the positive plate adopts at least one of Lithium Nickel Manganese Oxide (LNMO), lithium iron manganese phosphate or ternary materials (such as NCM11, NCM532, NCM622, NCM712, NCM811 and NCA); the negative plate adopts at least one of graphite, silicon-doped graphite or lithium metal, and the silicon content in the silicon-doped graphite is 2-40 wt%.
S2, primary liquid injection: and injecting a mixed solution into the dry cell, wherein the mixed solution comprises a monomer, a first initiator and a solvent, and the monomer contains at least two asymmetric double bonds. Specifically, the monomer comprises at least one of 1, 3-diisopropenylbenzene, 1, 3-hexadiene, 1, 4-poly (4, 8-2-methyl-1, 3, 7-nonyltriene), 1-hydroxy dicyclopentadiene, 5-isopropyl-2-methylcyclohexa-1, 3-diene, allene phosphonic acid, 1-methoxy-3-trimethylsiloxy-1, 3-butadiene, 3-methylene-7-methyl-1, 6-octadiene; the first initiator comprises at least one of azobisisobutyronitrile, dibenzoyl peroxide, azobisisoheptonitrile, 2-azobisisobutyronitrile. The method comprises the steps of carrying out a first treatment on the surface of the The solvent comprises at least one of dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, ethylene carbonate and propylene carbonate. In the mixed solution, the weight ratio of the monomers is 2-40 wt%, the weight ratio of the first initiator is 0.05-1 wt%, and the weight ratio of the solvent is 59-97 wt%.
S3, carrying out high-temperature prepolymerization to enable at least one double bond of the monomer to carry out prepolymerization reaction under the initiation of a first initiator so as to form a prepolymer. Wherein the high temperature prepolymerization temperature is 35-100deg.C, the prepolymerization time is 1-48 hours, and the high temperature prepolymerization temperature is 45 deg.C, 65 deg.C, 85 deg.C, etc., and the prepolymerization time is 24 hours, 48 hours, etc.
S4, drying at a high temperature so that residual solvent and monomer which does not undergo the prepolymerization reaction can be volatilized and discharged at a high temperature. Wherein the high temperature drying temperature is 60-100 ℃ and the drying time is 24-72 hours. Illustratively, the high temperature drying temperature is 60 ℃, 72 ℃, 85 ℃ and the like, and the drying time is 24 hours, 36 hours, 48 hours, 60 hours, 72 hours and the like.
S5, secondary liquid injection: injecting part of electrolyte into the dry cell; wherein the electrolyte is EC, FEC, EMC, DEC, liPF 6 、DTD、LiPO 2 F 2 Mixing the materials according to the mass ratio of 15:5.5:44:18:15:2:0.5.
S6, standing uniformly, forming and aging;
s7, three liquid injection: injecting a second initiator and the rest electrolyte into the dry cell; the second initiator includes at least one of azobisisobutyronitrile, dibenzoyl peroxide, azobisisoheptonitrile, 2-azobisisobutyronitrile, and the second initiator is different from the first initiator.
And S8, aging and polymerizing at high temperature to form a gel polymer, thus obtaining the semi-solid battery. Wherein the high temperature polymerization temperature is 60-100 ℃ and the time is 24-72 hours. Illustratively, the high temperature polymerization temperature is 60 ℃, 65 ℃, 85 ℃ and the like, and the high temperature polymerization time is 24 hours, 36 hours, 48 hours, 72 hours and the like.
The electrolyte of the secondary injection and the electrolyte of the tertiary injection are the same, the electrolyte of the secondary injection accounts for 70-95 wt% of the total electrolyte, the electrolyte of the tertiary injection accounts for 5-30 wt% of the total electrolyte, and the total electrolyte is the sum of the electrolyte of the secondary injection and the electrolyte of the tertiary injection.
In the step S2, when the liquid is injected once, as the injected monomer contains at least two asymmetric double bonds, the difference of the activity intensity of different double bonds exists, so that the polymerization degree and the polymerization time of different double bonds can be controlled through different initiation conditions, and the polymerization sequence of different double bonds can be controlled conveniently; then, in the high-temperature prepolymerization in the step S3, firstly initiating a relatively active double bond through an initiator to polymerize so as to form a prepolymer; removing the residual solvent and the monomer which do not participate in the reaction after the pre-polymerization reaction through the step S4 so as to reduce the residual quantity of the monomer in the later stage; then aging (small-rate charging) is carried out after part of electrolyte is injected in the steps S5 and S6, so that a solvation structure can be formed between the prepolymer and lithium ions in the electrolyte, the uniformity of the concentration of the prepolymer in the electrolyte and the wettability of the prepolymer in the electrode plate are improved through the movement of the lithium ions, and the consistency of the subsequent internal solution is further ensured; and through formation and aging after secondary liquid injection, the uniform mixing of the electrolyte and the prepolymer can be ensured, and the phenomenon that the prepolymer in the gap between the positive electrode and the negative electrode prevents the electrolyte from being immersed can be avoided; and finally, carrying out three-time liquid injection, aging and high-temperature polymerization through the step S7 and the step S8 so as to polymerize the less active double bonds in the monomer to form a gel network, closely attaching positive and negative interfaces, further improving the interface contact of the electrolyte and improving the electrochemical performance of the battery.
The dry battery cell adopts a conventional dry battery cell preparation process, wherein an anode sheet adopts NCM811 material, and a cathode adopts silicon-oxygen doped graphite material. In particular, the method comprises the steps of,
firstly, preparing positive electrode slurry, wherein the mass ratio of the components of the positive electrode slurry is ternary material (LiNi 0.8 Co 0.1 Mn 0.1 O 2 ) Conductive carbon black (Super P) Carbon Nano Tube (CNT) binder (PVDF-5130) =96:1.2:1.6:1.2, coating the positive electrode slurry on aluminum foil, and rolling and cutting to obtain the positive electrode plate.
And then preparing negative electrode slurry, wherein the mass ratio of the components of the negative electrode slurry is graphite, silicon oxide, carbon Nano Tubes (CNT), binder (sodium carboxymethylcellulose (CMC)) and binder (styrene butadiene rubber (SBR) =90:5:2:1.2:1.8), coating the negative electrode slurry on copper foil, and rolling and cutting to obtain the negative electrode plate.
And finally, laminating the positive plate, the diaphragm and the negative plate, wherein the diaphragm adopts a PE diaphragm (an alumina layer of 3 mu m, a base film of 9 mu m and an alumina layer of 3 mu m), hot-pressing the bare cell after lamination, welding the tab, and putting the bare cell into a shell to prepare the dry cell.
Example 1
5g of 1, 3-hexadiene monomer and 0.05g of initiator dibenzoyl peroxide are added into a methyl ethyl carbonate solvent, and the mixture is stirred for 30min to obtain a mixed solution, wherein the total mass of the mixed solution is 100g;
the mixed solution is added into a dry cell and is sealed by filling in a glove box with the water-oxygen content of less than 0.1 ppm. Soaking the sealed battery cell for 48 hours at room temperature, and then placing the battery cell in a drying oven at 65 ℃ for prepolymerization for 6 hours; cutting the prepolymerized battery cell, and placing the battery cell in a recyclable vacuum oven at 85 ℃ for 72 hours to dry the monomer and solvent which do not participate in the reaction;
then the secondary injection is carried out on the battery cell, and the electrolyte is prepared into EC, FEC, EMC, DEC, liPF components 6 、DTD、LiPO 2 F 2 (mass ratio is 15:5.5:44:18:15:2:0.5), 85wt% of the total electrolyte is injected, after the electrolyte is immersed for 48 hours at room temperature, the battery is subjected to formation at 25 ℃, and aging is carried out for 24 hours at 45 ℃;
breaking the aged battery cell at one side far away from the pole piece, then mixing an initiator azodiisobutyronitrile and the rest electrolyte (namely 15wt% of the total electrolyte) in a glove box with water-oxygen content lower than 0.01ppm according to a mass ratio of 1:1000, and then injecting the mixed solution into the aged battery cell;
and (3) fully soaking for 48 hours at 20 ℃, carrying out high-temperature polymerization for 36 hours at 60 ℃, and carrying out capacity division on the battery at 0.33c multiplying power to obtain the semi-solid battery.
Example 2
5g of 1, 3-diisopropenylbenzene monomer and 0.05g of initiator azodiisobutyronitrile are added into diethyl carbonate solvent, and the mixture is stirred for 30min to obtain a mixed solution, wherein the total mass of the mixed solution is 100g;
the mixed solution is added into a dry cell and is sealed by filling in a glove box with the water-oxygen content of less than 0.1 ppm. Soaking the sealed battery cell for 48 hours at room temperature, and then placing the battery cell in a drying oven at 65 ℃ for prepolymerization for 3 hours; cutting the prepolymerized battery cell, and placing the battery cell in a recyclable vacuum oven at 65 ℃ for 72 hours to dry the monomer and solvent which do not participate in the reaction;
then the secondary injection is carried out on the battery cell, and the electrolyte is prepared into EC, FEC, EMC, DEC, liPF components 6 、DTD、LiPO 2 F 2 (mass ratio is 15:5.5:44:18:15:2:0.5), 85wt% of the total electrolyte is injected, after the electrolyte is immersed for 48 hours at room temperature, the battery is subjected to formation at 25 ℃, and aging is carried out for 24 hours at 45 ℃;
breaking the aged battery cell at one side far away from the pole piece, then mixing initiator dibenzoyl peroxide with the rest electrolyte (namely 15wt% of the total electrolyte) in a glove box with water oxygen content lower than 0.01ppm according to a mass ratio of 1:1000, and then injecting the mixed solution into the aged battery cell;
and (3) fully soaking for 48 hours at 20 ℃, then carrying out high-temperature polymerization for 36 hours at 70 ℃, and carrying out capacity division on the battery at a rate of 0.33c to obtain the semi-solid battery.
Example 3
Adding 5g of methyl methacrylate monomer, 0.5g of propylene diene phosphonic acid monomer and 0.05g of initiator azodiisobutyronitrile into a diethyl carbonate solvent, and stirring for 30min to obtain a mixed solution, wherein the total mass of the mixed solution is 100g;
the mixed solution is added into a dry cell and is sealed by filling in a glove box with the water-oxygen content of less than 0.1 ppm. Soaking the sealed battery cell for 48 hours at room temperature, and then placing the battery cell in a drying oven at 65 ℃ for prepolymerization for 3 hours; cutting the prepolymerized battery cell, and placing the battery cell in a recyclable vacuum oven at 65 ℃ for 72 hours to dry the monomer and solvent which do not participate in the reaction;
then the secondary injection is carried out on the battery cell, and the electrolyte is prepared into EC, FEC, EMC, DEC, liPF components 6 、DTD、LiPO 2 F 2 (mass ratio is 15:5.5:44:18:15:2:0.5), 85wt% of the total electrolyte is injected, after the electrolyte is immersed for 48 hours at room temperature, the battery is subjected to formation at 25 ℃, and aging is carried out for 24 hours at 45 ℃;
breaking the aged battery cell at one side far away from the pole piece, then mixing initiator dibenzoyl peroxide with the rest electrolyte (namely 15wt% of the total electrolyte) in a glove box with water oxygen content lower than 0.01ppm according to a mass ratio of 1:1000, and then injecting the mixed solution into the aged battery cell;
and (3) fully soaking at 20 ℃ for 48 hours, then carrying out high-temperature polymerization at 60 ℃ for 48 hours, and carrying out capacity division on the battery at 0.33c multiplying power to obtain the semi-solid battery.
Example 4
This embodiment differs from embodiment 3 in that: the allenylphosphonic acid monomer was replaced with a 3-methylene-7-methyl-1, 6-octadiene monomer.
Example 5
This embodiment differs from embodiment 3 in that: methyl methacrylate monomer was replaced with trifluoroethyl methacrylate monomer, and the malonyl phosphonic acid monomer was replaced with 1-methoxy-3-trimethylsiloxy-1, 3-butadiene.
Comparative example 1
Preparing electrolyte with the components of EC, FEC, EMC, DEC, liPF 6 、DTD、LiPO 2 F 2 (mass ratio of 15:5.5:44:18:15:2:0.5);
injecting liquid for the first time into the dry battery core, injecting 85wt% of the total amount of electrolyte, soaking for 48 hours at room temperature, performing formation at 25 ℃ on the battery, and aging for 24 hours at 45 ℃;
performing secondary injection on the aged battery cell, and injecting 15wt% of the total electrolyte;
and (3) fully soaking at 20 ℃ for 48 hours, standing at a high temperature of 60 ℃ for 48 hours, and carrying out capacity division on the battery at a multiplying power of 0.33c to obtain the battery.
Comparative example 2
Preparing electrolyte containing monomer, wherein the component is EC, FEC, EMC, DEC, liPF 6 、DTD、LiPO 2 F 2 Methyl methacrylate monomer, allenyl phosphonic acid monomer, azobisisobutyronitrile (mass ratio 15:5.5:44:18:15:2:0.5:5:0.5:0.05);
injecting liquid for the first time into the dry battery core, injecting 85wt% of the total amount of electrolyte, soaking for 48 hours at room temperature, performing formation at 25 ℃ on the battery, and aging for 24 hours at 45 ℃;
performing secondary injection on the aged battery cell, and injecting 15wt% of the total electrolyte;
and (3) fully soaking at 20 ℃ for 48 hours, standing at a high temperature of 60 ℃ for 48 hours, and carrying out capacity division on the battery at a multiplying power of 0.33c to obtain the battery.
Test examples
The batteries of examples 1 to 5 and comparative examples 1 to 2 were subjected to cycle performance and needling test, wherein the cycle test was an oven test at 25 ℃, the charge and discharge rate was 0.5C, the charge and discharge schedule was constant-current constant-voltage charge and constant-current discharge, and the test voltage range was 2.7 to 4.2V; the needling test was performed using national standard GB/T31485-2015, and the test results are shown in Table 1.
Table 1 test results for examples 1 to 5 and comparative examples 1 to 2
As can be seen from table 1: compared with the pure electrolyte battery of comparative example 1, the semi-solid battery formed by the three-step liquid injection in examples 1 to 5 has only a small increase in internal resistance, but the electrolyte after in-situ polymerization has better compatibility with the electrode plate interface, and particularly the battery of example 3 has a small increase in cycle performance; compared with the semi-solid battery of comparative example 2, the electrical cycle performance of the semi-solid batteries of examples 1 to 5 is greatly improved, and the adhesion of the electrode sheet and the separator is stronger due to the adhesion of the gel, so that the heat shrinkage of the separator is reduced, thereby improving the safety performance of the battery cell.
The above embodiments are only for illustrating the technical concept and features of the present invention, and are intended to enable those skilled in the art to understand the content of the present invention and to implement the same, but are not intended to limit the scope of the present invention, and all equivalent changes or modifications made according to the spirit of the present invention should be included in the scope of the present invention.
Claims (13)
1. The preparation method of the in-situ polymerization semi-solid battery is characterized by comprising the following steps of:
s1, assembling a dry cell;
s2, primary liquid injection: injecting a mixed solution into the dry cell, wherein the mixed solution comprises a monomer, a first initiator and a solvent, and the monomer contains at least two asymmetric double bonds;
s3, carrying out high-temperature prepolymerization to enable at least one double bond of the monomer to carry out prepolymerization reaction under the initiation of a first initiator so as to form a prepolymer;
s4, drying at a high temperature to volatilize and discharge the residual solvent and the monomer which does not undergo the prepolymerization reaction at a high temperature;
s5, secondary liquid injection: injecting part of electrolyte into the dry cell;
s6, standing uniformly, forming and aging;
s7, three liquid injection: injecting a second initiator and the rest electrolyte into the dry cell;
and S8, aging and polymerizing at high temperature to form a gel polymer, thus obtaining the semi-solid battery.
2. The method according to claim 1, wherein in step S2, the monomer comprises at least one of 1, 3-diisopropenylbenzene, 1, 3-hexadiene, 1, 4-poly (4, 8-2-methyl-1, 3, 7-nonyltriene), 1-hydroxydicyclopentadiene, 5-isopropyl-2-methylcyclohexa-1, 3-diene, allene phosphonic acid, 1-methoxy-3-trimethylsiloxy-1, 3-butadiene, 3-methylene-7-methyl-1, 6-octadiene.
3. The method according to claim 2, wherein in step S2, the first initiator comprises at least one of azobisisobutyronitrile, dibenzoyl peroxide, azobisisoheptonitrile, 2-azobisisobutyronitrile.
4. The production method according to claim 1, wherein in step S2, the solvent includes at least one of dimethyl carbonate, diethyl carbonate, methylethyl carbonate, ethylene carbonate, propylene carbonate.
5. The preparation method according to claim 1, wherein the weight ratio of the monomer in the mixed solution is 2 to 40wt%, the weight ratio of the first initiator is 0.05 to 1wt%, and the weight ratio of the solvent is 59 to 97wt%.
6. The process according to any one of claims 1 to 5, wherein in step S3, the high temperature prepolymerization is carried out at a temperature of 35 to 100℃for a period of 1 to 48 hours.
7. The preparation method according to claim 1, wherein in step S4, the high temperature drying is performed at 60 to 100 ℃ for 24 to 72 hours.
8. The preparation method according to claim 1, wherein the electrolyte of the secondary injection is 70-95 wt% of the total electrolyte, and the electrolyte of the tertiary injection is 5-30 wt% of the total electrolyte.
9. The production method according to claim 1, wherein the second initiator comprises at least one of azobisisobutyronitrile, dibenzoyl peroxide, azobisisoheptonitrile, 2-azobisisobutyronitrile, and the second initiator is different from the first initiator.
10. The method according to claim 1, wherein the high-temperature polymerization is carried out at a temperature of 60 to 100℃for 24 to 72 hours in step S8.
11. The method of claim 1, wherein step S1 comprises: and respectively preparing a positive plate, a negative plate and a diaphragm, and then assembling the positive plate, the negative plate and the diaphragm into a shell to prepare the dry battery cell.
12. The method of manufacturing according to claim 11, wherein the positive electrode sheet comprises at least one of lithium nickel manganese oxide, lithium manganese iron phosphate, or ternary material; the negative plate comprises at least one of graphite, silicon-doped graphite or lithium metal, wherein the silicon content of the silicon-doped graphite is 2-40 wt%.
13. An in situ polymerized semi-solid battery prepared by the method of any one of claims 1-12.
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