CN113823763A - Polymer electrolyte membrane coated metal oxalate composite electrode and semi-solid lithium ion battery - Google Patents

Polymer electrolyte membrane coated metal oxalate composite electrode and semi-solid lithium ion battery Download PDF

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CN113823763A
CN113823763A CN202111143107.8A CN202111143107A CN113823763A CN 113823763 A CN113823763 A CN 113823763A CN 202111143107 A CN202111143107 A CN 202111143107A CN 113823763 A CN113823763 A CN 113823763A
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polymer electrolyte
metal oxalate
electrolyte membrane
lithium ion
electrode
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张克宇
姚耀春
崔丁方
高耕
宋廷玉
杨斌
马文会
杨桂玲
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Kunming University of Science and Technology
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Abstract

The invention discloses a polymer electrolyte membrane coated metal oxalate composite electrode and a semi-solid lithium ion battery, belonging to the technical field of lithium ion batteries; the polyvinylidene fluoride-hexafluoropropylene copolymer (PVDF-HFP) with higher ionic conductivity is mixed with N-methyl pyrrolidone (NMP) organic solution, and the mixture is stirred until the polyvinylidene fluoride-hexafluoropropylene copolymer (PVDF-HFP) and the N-methyl pyrrolidone (NMP) are completely dissolved; then adding the lithium bis (trifluoromethanesulfonyl imide) (LiTFSI) polymer electrolyte into the solution, further stirring the solution until the solution is uniformly dispersed to obtain a sol polymer electrolyte, defoaming the sol polymer electrolyte, coating the electrolyte on the surface of a metal oxalate electrode, and drying the metal oxalate electrode in a vacuum drying oven to obtain a metal oxalate negative electrode coated with a polymer electrolyte membrane; finally, a small amount of electrolyte is infiltrated on the surface of the polymer electrolyte membrane to form a gel layer, and the semi-solid lithium ion battery is assembled according to a conventional method. The invention effectively solves the problems of high irreversible capacity, poor cycle performance and the like of the metal oxalate-based lithium ion battery.

Description

Polymer electrolyte membrane coated metal oxalate composite electrode and semi-solid lithium ion battery
Technical Field
The invention relates to a metal oxalate composite electrode coated with a polymer electrolyte membrane and a semi-solid lithium ion battery, belonging to the technical field of lithium ion batteries.
Background
In recent years, lithium ion batteries have been widely used as a new high-energy green chemical power source in new energy vehicles, portable mobile devices, large base stations, and the like. However, the high-power and large-capacity lithium ion power battery used in the electric vehicle is troubled by the problems of volume density, price and safety, and the lithium ion battery still faces a great challenge. Compared with other alternative materials, the metal oxalate based on the conversion reaction has the advantages of high reversible capacity, excellent cycle performance, abundant resources, environmental friendliness, high safety and the like. However, decomposition of the electrolyte during charge and discharge forms a large number of stable organic layers and SEI films on the surface of active material particles, which results in a metal oxalate negative electrode material having a high irreversible capacity and poor cycle performance.
Currently, the improvement of oxalate performance is mainly focused on the design of the surface structure of the active material particles, aiming at the above-mentioned drawbacks. Wherein the metal oxide (e.g. Al)2O3、Fe2O3、ZnO、SiOx、TiO2Etc.) have been widely reported to be used for surface coating of electrode materials to change the electrochemical cycling stability of the materials. This approach not only relieves Li+Unstable SEI formed in the process of rapid ion embedding/ion releasing avoids pulverization of particles caused by volume effect, reasonable composite material micro-nano structure design can be relied on, and material characteristics can be further improved by utilizing mutual synergistic effect between materials. However, the surface structure of the active material particles is designed only to enhance the stability of the organic layer and the SEI film, and the disadvantage of high irreversible capacity of the material cannot be improved well. In the invention, from the angle of optimizing the surface structure of the electrode material, a stable and well-contacted deposition film is formed on the surface of the electrode through the novel polymer electrolyte, so that an unstable organic substance layer caused by the decomposition of the electrolyte can be properly inhibited, and the capacity and the cycle life of the lithium ion battery are improved.
Disclosure of Invention
Aiming at the defects of the technology, the invention provides a metal oxalate composite electrode coated by a polymer electrolyte membrane and a semi-solid lithium ion battery according to the problems of high irreversible capacity, poor cycle performance and the like of a lithium ion battery metal oxalate negative electrode material.
The invention adopts a method of scraping and coating an electrode interface to tightly deposit the novel polymer electrolyte on the surface of the ferrous oxalate negative electrode. Firstly, uniformly mixing polyvinylidene fluoride-hexafluoropropylene copolymer (PVDF-HFP) and N-methyl pyrrolidone (NMP) organic solution, adding lithium bis (trifluoromethanesulfonyl imide) (LiTFSI) polymer, and stirring until the polymer is completely dissolved to obtain sol polymer electrolyte; then uniformly coating the polymer electrolyte on a metal oxalate copper foil electrode by a blade coating method; during the assembly of the battery, a small amount of electrolyte is used for infiltrating the interface of the polymer electrolyte and the positive electrode so as to form a stable gel layer. The method for modifying the surface of the polymer electrolyte can avoid higher irreversible capacity caused by the enrichment of the electrolyte on the surface of the material particles, reduce the use of a diaphragm in the battery assembly process and further increase the energy density of the battery.
The technical scheme of the invention is as follows: a polymer electrolyte membrane coated metal oxalate composite electrode and a semi-solid lithium ion battery are prepared by the following steps:
(1) sequentially adding polyvinylidene fluoride-hexafluoropropylene copolymer and N-methyl pyrrolidone organic solution into a sealed container, stirring at normal temperature until the polyvinylidene fluoride-hexafluoropropylene copolymer and N-methyl pyrrolidone organic solution are completely dissolved to obtain colorless and transparent colloidal solution, adding the bis-trifluoromethanesulfonyl imide lithium polymer into the colloidal solution, continuously stirring for 12-48 h, and then defoaming to obtain a sol polymer electrolyte, wherein the concentration of the polyvinylidene fluoride-hexafluoropropylene copolymer is 0.05-2 g/mL, and the mass ratio of the polyvinylidene fluoride-hexafluoropropylene copolymer (PVDF-HFP) to the bis-trifluoromethanesulfonyl imide Lithium (LiTFSI) polymer is 10: 0-5: 5;
(2) weighing a metal oxalate negative electrode material, a Super-P conductive agent and polyvinylidene fluoride according to the mass ratio of 6:3: 1-9: 0.5:0.5, mixing and grinding for 5-30 min, adding an N-methyl-2-pyrrolidone solvent into the mixture, continuously grinding for 5-30 min to obtain a viscous mixture, uniformly coating the viscous mixture on a copper foil, and drying in vacuum for 12-24 h at the temperature of 80-120 ℃ to obtain a metal oxalate negative electrode, wherein the mass ratio of the N-methyl-2-pyrrolidone solvent to the mixture is 2: 1-10: 1, and the metal oxalate negative electrode material is ferrous oxalate, cobalt oxalate, manganese oxalate, nickel oxalate, tin oxalate or copper oxalate and other metal oxalates.
(3) Reinstalling the metal oxalate negative electrode coated in the step (2) on a coating machine, adjusting the distance between a scraper and the electrode to be 0.01-0.05 mm, coating the sol polymer electrolyte obtained in the step (1) on the surface of the oxalate negative electrode by a blade coating method, then drying in vacuum for 12-24 hours at the temperature of 80-120 ℃ to obtain a metal oxalate composite electrode coated with a polymer electrolyte membrane, and rolling and cutting the electrode to obtain a negative pole piece, wherein the thickness of the polymer electrolyte membrane is 0.01-0.05 mm;
(4) dripping electrolyte on the metal oxalate composite electrode coated with the polymer electrolyte membrane prepared in the step (3) by using a liquid-transferring gun in a glove box filled with argon gas, uniformly dispersing the electrolyte, and then adding the metal oxalate composite electrodeThe negative pole piece, the positive pole piece and the foam nickel net are assembled into a button cell, a gel layer is formed near the interface of the polymer electrolyte membrane and the positive pole piece, and thus the semi-solid lithium ion battery with the metal oxalate negative interface improved by the polymer electrolyte membrane is obtained, wherein the ratio of the dropping amount of the electrolyte to the area of the polymer electrolyte interface is 0.02-0.05 mL/cm2Wherein the electrolyte is prepared by mixing Ethylene Carbonate (EC) and diethyl carbonate (DEC) at a volume ratio of 1:1, and adding LiPF6Material, formulation LiPF6Electrolyte with the concentration of 1 mol/L.
The invention has the beneficial effects that:
the invention prepares a metal oxalate composite electrode coated with a polymer electrolyte membrane and a semi-solid lithium ion battery by an electrode interface blade coating method. The invention utilizes the novel polymer electrolyte membrane to coat the interface of the metal oxalate electrode, relieves the irreversible capacity caused by the enrichment of electrolyte decomposition products on the surface of material particles, enhances the stability of the anode and cathode interfaces and the electrolyte layer through the gel layer, and provides good interface characteristics for improving the capacity retention and the cycle performance of the material. In addition, the novel polymer electrolyte membrane can also serve as a separator and a solid electrolyte, enhancing the energy density of the battery.
Drawings
FIG. 1 is a schematic diagram of a semi-solid lithium ion battery of the present invention;
FIG. 2 is a scanning electron micrograph of the interface of a ferrous oxalate electrode prepared according to example 1 of the present invention, wherein a is a composite electrode coated with a polymer electrode film and b is an electrode not coated with a polymer electrode film;
fig. 3 is a cyclic voltammogram of a semi-solid battery prepared in example 2 of the present invention, wherein a is a first scan cyclic voltammogram and b is a 2 to 6 scan cyclic voltammogram;
fig. 4 is a graph comparing the cycle performance of the polymer electrode film-coated ferrous oxalate composite electrode and the semi-solid battery prepared in examples 1, 2, and 3 of the present invention with that of the conventional lithium ion battery.
Detailed Description
The invention is described in more detail below with reference to the figures and examples, without limiting the scope of the invention.
Example 1: the preparation method of the metal oxalate composite electrode coated on the polymer electrolyte membrane and the semi-solid lithium ion battery comprises the following steps:
(1) sequentially adding polyvinylidene fluoride-hexafluoropropylene copolymer and N-methyl pyrrolidone organic solution into a sealed container, stirring at normal temperature until the polyvinylidene fluoride-hexafluoropropylene copolymer and the N-methyl pyrrolidone organic solution are completely dissolved to obtain colorless and transparent colloidal solution, wherein the concentration of the polyvinylidene fluoride-hexafluoropropylene copolymer is 0.1 g/mL; adding the lithium bistrifluoromethylsulfonyl imide polymer into the colloidal solution, continuously stirring for 24 hours, and then carrying out defoaming treatment to obtain a sol polymer electrolyte, wherein the mass ratio of the polyvinylidene fluoride-hexafluoropropylene copolymer (PVDF-HFP) to the lithium bistrifluoromethylsulfonyl imide (LiTFSI) polymer is 7: 3;
(2) weighing a ferrous oxalate material, a Super-P conductive agent and polyvinylidene fluoride according to a mass ratio of 6:3:1, mixing and grinding for 15min, adding an N-methyl-2-pyrrolidone solvent into the mixture, continuously grinding for 15min to obtain a viscous mixture, uniformly coating the viscous mixture on a copper foil, and drying in vacuum for 12h at 80 ℃ to obtain a ferrous oxalate negative electrode, wherein the mass ratio of the added N-methyl-2-pyrrolidone solvent to the mixture is 2: 1;
(3) reinstalling the ferrous oxalate electrode coated in the step (2) on a coating machine, adjusting the distance between a scraper and the electrode to be 0.01mm, coating the sol polymer electrolyte obtained in the step (1) on the surface of the ferrous oxalate electrode by a blade coating method, then drying in vacuum for 12 hours at the temperature of 80 ℃ to obtain a ferrous oxalate composite electrode coated with a polymer electrolyte membrane, wherein the thickness of the polymer electrolyte membrane is 0.01mm, then rolling the electrode, and cutting into a required size to obtain a negative pole piece;
(4) ethylene Carbonate (EC) and diethyl carbonate (DEC) were mixed in a volume ratio of 1:1, and LiPF was added thereto6Material, formulation LiPF6Electrolyte with the concentration of 1 mol/L; in a glove box filled with argon, a pipette is used to dripAdding the electrolyte solution to the ferrous oxalate composite electrode coated with the polymer electrolyte membrane prepared in the step (3) and uniformly dispersing the electrolyte solution, wherein the ratio of the dropping amount of the electrolyte solution to the interfacial area of the polymer electrolyte is 0.03mL/cm2And then assembling the negative pole piece, the positive pole piece and the foam nickel net into a button cell by a conventional method, and forming a gel layer near the interface of the polymer electrolyte membrane and the positive pole piece so as to obtain the semi-solid lithium ion battery with the ferrous oxalate negative interface improved by the polymer electrolyte membrane.
Fig. 1 is a schematic diagram of a semi-solid battery having a polymer electrolyte membrane to improve the ferrous oxalate electrode interface.
Fig. 2 is an SEM image of the new polymer electrolyte membrane improving ferrous oxalate negative electrode interface, wherein fig. 2a is a composite electrode coated with the new polymer electrode membrane, and fig. 2b is an electrode not coated with the new polymer electrode membrane, and it is apparent from the figure that the active material coating and the electrolyte coating have better binding ability at the cross section of the electrode.
Example 2: the preparation method of the ferrous oxalate composite electrode coated with the polymer electrolyte membrane and the semi-solid lithium ion battery comprises the following steps:
(1) sequentially adding polyvinylidene fluoride-hexafluoropropylene copolymer and N-methyl pyrrolidone organic solution into a sealed container, stirring at normal temperature until the polyvinylidene fluoride-hexafluoropropylene copolymer and the N-methyl pyrrolidone organic solution are completely dissolved to obtain colorless and transparent colloidal solution, wherein the concentration of the polyvinylidene fluoride-hexafluoropropylene copolymer is 0.05 g/mL; in the embodiment, a lithium bistrifluoromethanesulfonylimide polymer is not added, namely the mass ratio of polyvinylidene fluoride-hexafluoropropylene copolymer (PVDF-HFP) to lithium bistrifluoromethylsulfonylimide (LiTFSI) polymer is 10:0, and a sol polymer electrolyte is obtained through defoaming treatment;
(2) weighing a ferrous oxalate material, a Super-P conductive agent and polyvinylidene fluoride according to a mass ratio of 9:0.5:0.5, mixing and grinding for 5min, adding an N-methyl-2-pyrrolidone solvent into the mixture, continuously grinding for 5min to obtain a viscous mixture, uniformly coating the viscous mixture on a copper foil, and drying in vacuum for 24h at 100 ℃ to obtain a ferrous oxalate negative electrode, wherein the mass ratio of the added N-methyl-2-pyrrolidone solvent to the mixture is 10: 1; (ii) a
(3) Reinstalling the ferrous oxalate electrode coated in the step (2) on a coating machine, adjusting the distance between a scraper and the electrode to be 0.03mm, coating the sol polymer electrolyte obtained in the step (1) on the surface of the ferrous oxalate electrode by a blade coating method, then drying in vacuum for 24 hours at the temperature of 100 ℃ to obtain a ferrous oxalate composite electrode coated with a polymer electrolyte membrane, wherein the thickness of the polymer electrolyte membrane is 0.03mm, then rolling the electrode, and cutting into a required size to obtain a negative pole piece;
(4) ethylene Carbonate (EC) and diethyl carbonate (DEC) were mixed in a volume ratio of 1:1, and LiPF was added thereto6Material, formulation LiPF6Electrolyte with the concentration of 1 mol/L; dripping the electrolyte on the ferrous oxalate composite electrode coated with the polymer electrolyte membrane prepared in the step (3) by using a liquid-transferring gun in a glove box filled with argon gas, and uniformly dispersing the electrolyte, wherein the ratio of the dripping amount of the electrolyte to the interfacial area of the polymer electrolyte is 0.02mL/cm2And then assembling the negative pole piece, the positive pole piece and the foam nickel net into a button cell by a conventional method, and forming a gel layer near the interface of the polymer electrolyte membrane and the positive pole piece so as to obtain the semi-solid lithium ion battery with the ferrous oxalate negative interface improved by the polymer electrolyte membrane.
The cyclic voltammetry test results for the semi-solid cells prepared in this example are shown in fig. 3. Wherein fig. 3a is a first scanning cyclic voltammetry graph, and fig. 3b is a 2 to 6 scanning cyclic voltammetry graph, it can be clearly seen that the intensity of the conversion reaction of the material at 0.75V is continuously enhanced as the cycle progresses, which indicates that the electrochemical reaction activity of the material can be significantly improved by the polymer electrolyte membrane.
Example 3: the preparation method of the polymer electrolyte membrane coated metal oxalate composite electrode and the semi-solid lithium ion battery comprises the following steps:
(1) sequentially adding polyvinylidene fluoride-hexafluoropropylene copolymer and N-methyl pyrrolidone organic solution into a sealed container, stirring at normal temperature until the polyvinylidene fluoride-hexafluoropropylene copolymer and the N-methyl pyrrolidone organic solution are completely dissolved to obtain colorless and transparent colloidal solution, wherein the concentration of the polyvinylidene fluoride-hexafluoropropylene copolymer is 2 g/mL; adding the lithium bistrifluoromethylsulfonyl imide polymer into the colloidal solution, continuously stirring for 48 hours, and then carrying out defoaming treatment to obtain a sol polymer electrolyte, wherein the mass ratio of the polyvinylidene fluoride-hexafluoropropylene copolymer (PVDF-HFP) to the lithium bistrifluoromethylsulfonyl imide (LiTFSI) polymer is 5: 5;
(2) weighing a ferrous oxalate material, a Super-P conductive agent and polyvinylidene fluoride according to the mass ratio of 7:2:0.7, mixing and grinding for 30min, adding an N-methyl-2-pyrrolidone solvent into the mixture, continuously grinding for 30min to obtain a viscous mixture, uniformly coating the viscous mixture on a copper foil, and drying in vacuum for 20h at 120 ℃ to obtain a ferrous oxalate negative electrode, wherein the mass ratio of the added N-methyl-2-pyrrolidone solvent to the mixture is 5: 1;
(3) reinstalling the ferrous oxalate electrode coated in the step (2) on a coating machine, adjusting the distance between a scraper and the electrode to be 0.05mm, coating the sol polymer electrolyte obtained in the step (1) on the surface of the ferrous oxalate electrode by a blade coating method, then drying in vacuum for 20 hours at 120 ℃ to obtain a ferrous oxalate composite electrode coated with a polymer electrolyte membrane, wherein the thickness of the polymer electrolyte membrane is 0.05mm, then rolling the electrode, and cutting into a required size to obtain a negative pole piece;
(4) ethylene Carbonate (EC) and diethyl carbonate (DEC) were mixed in a volume ratio of 1:1, and LiPF was added thereto6Material, formulation LiPF6Dropwise adding the electrolyte with the concentration of 1mol/L onto the ferrous oxalate composite electrode coated with the polymer electrolyte membrane prepared in the step (3) by using a liquid-transferring gun in a glove box filled with argon gas, and uniformly dispersing the electrolyte, wherein the ratio of the dropping amount of the electrolyte to the interfacial area of the polymer electrolyte is 0.05mL/cm2Then assembling the negative pole piece, the positive pole piece and the foam nickel net into a button cell by a conventional method, and forming a gel layer near the interface of the polymer electrolyte membrane and the positive pole piece so as to obtain the ferrous oxalate negative pole with the improved polymer electrolyte membraneAn interfacial semi-solid lithium ion battery.
Comparing the cycle performance of the semi-solid state battery prepared in this example and examples 1 and 2 with that of the conventional lithium ion battery, as shown in fig. 4, it can be seen that the semi-solid state battery exhibits better reversible capacity retention and excellent cycle stability compared to the conventional lithium ion battery.
While the present invention has been described in detail with reference to the embodiments shown in the drawings, the present invention is not limited to the embodiments, and various changes can be made without departing from the spirit and scope of the present invention.

Claims (5)

1. A metal oxalate composite electrode coated with a polymer electrolyte membrane and a semi-solid lithium ion battery are characterized by comprising the following specific steps:
(1) sequentially adding polyvinylidene fluoride-hexafluoropropylene copolymer and N-methyl pyrrolidone organic solution into a sealed container, stirring at normal temperature until the polyvinylidene fluoride-hexafluoropropylene copolymer and the N-methyl pyrrolidone organic solution are completely dissolved to obtain colorless and transparent colloidal solution, adding the bis (trifluoromethanesulfonyl) imide lithium polymer into the colloidal solution, continuously stirring for 12-48 h, and then defoaming to obtain sol polymer electrolyte;
(2) weighing a metal oxalate negative electrode material, a Super-P conductive agent and polyvinylidene fluoride according to the mass ratio of 6:3: 1-9: 0.5:0.5, mixing and grinding for 5-30 min, adding an N-methyl-2-pyrrolidone solvent into the mixture, continuously grinding for 5-30 min to obtain a viscous mixture, uniformly coating the viscous mixture on a copper foil, and drying in vacuum for 12-24 h at the temperature of 80-120 ℃ to obtain a metal oxalate negative electrode, wherein the mass ratio of the N-methyl-2-pyrrolidone solvent to the mixture is 2: 1-10: 1;
(3) reinstalling the metal oxalate negative electrode coated in the step (2) on a coating machine, adjusting the distance between a scraper and the electrode to be 0.01-0.05 mm, coating the sol polymer electrolyte obtained in the step (1) on the surface of the oxalate negative electrode by a blade coating method, then drying in vacuum for 12-24 hours at the temperature of 80-120 ℃ to obtain a metal oxalate composite electrode coated with a polymer electrolyte membrane, and rolling and cutting the electrode to obtain a negative pole piece;
(4) and (3) dripping electrolyte on the metal oxalate composite electrode coated on the polymer electrolyte membrane prepared in the step (3) by using a liquid-transferring gun in a glove box filled with argon gas, uniformly dispersing the metal oxalate composite electrode, assembling the negative electrode plate, the positive electrode plate and a foam nickel net into a button cell, and forming a gel layer near the interface of the polymer electrolyte membrane and the positive electrode plate so as to obtain the semi-solid lithium ion battery with the metal oxalate negative electrode interface improved by the polymer electrolyte membrane.
2. The polymer electrolyte membrane coated metal oxalate composite electrode and the semi-solid lithium ion battery according to claim 1, wherein: the concentration of the polyvinylidene fluoride-hexafluoropropylene copolymer in the step (1) is 0.05-2 g/mL; the mass ratio of the polyvinylidene fluoride-hexafluoropropylene copolymer to the lithium bis (trifluoromethanesulfonyl) imide polymer is 10: 0-5: 5.
3. The polymer electrolyte membrane coated metal oxalate composite electrode and the semi-solid lithium ion battery according to claim 1, wherein: the thickness of the polymer electrolyte membrane in the step (3) is 0.01 mm-0.05 mm.
4. The polymer electrolyte membrane coated metal oxalate composite electrode and the semi-solid lithium ion battery according to claim 1, wherein: the ratio of the addition amount of the electrolyte liquid to the interfacial area of the polymer electrolyte in the step (4) is 0.02-0.05 mL/cm2。
5. The polymer electrolyte membrane coated metal oxalate composite electrode and the semi-solid lithium ion battery according to claim 1, wherein: the electrolyte in the step (4) is specifically prepared by mixing ethylene carbonate and diethyl carbonate according to the volume ratio of 1:1, and adding LiPF6Material, formulation LiPF6At a concentration of 1mol/LAnd (3) an electrolyte.
CN202111143107.8A 2021-09-28 2021-09-28 Polymer electrolyte membrane coated metal oxalate composite electrode and semi-solid lithium ion battery Pending CN113823763A (en)

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