CN112331827B - Large-current in-situ carbonization method for solid electrolyte anode - Google Patents

Large-current in-situ carbonization method for solid electrolyte anode Download PDF

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CN112331827B
CN112331827B CN202011161550.3A CN202011161550A CN112331827B CN 112331827 B CN112331827 B CN 112331827B CN 202011161550 A CN202011161550 A CN 202011161550A CN 112331827 B CN112331827 B CN 112331827B
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solid electrolyte
organic polymer
anode
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positive
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CN112331827A (en
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刘争
陈鹏飞
付兴杰
刘宝烨
原骏
江妙丽
沈文钟
冯杰仪
陶旺
彭章泉
汪达
邱振平
曾庆光
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Wuyi University
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    • H01—ELECTRIC ELEMENTS
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    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
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    • H—ELECTRICITY
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    • 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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
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    • H01M4/0407—Methods of deposition of the material by coating on an electrolyte layer
    • H—ELECTRICITY
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    • 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
    • H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
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    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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Abstract

The invention provides a high-current in-situ carbonization method for a solid electrolyte anode, which comprises the following specific steps: polishing and grinding the solid electrolyte matrix; mixing an organic polymer and a positive active material, and then transferring the mixture into a glove box filled with Ar gas atmosphere; uniformly coating the slurry on the surface of the solid electrolyte in a glove box; then, a transient large current is applied to partially carbonize the organic polymer coated on the surface of the solid electrolyte. According to the invention, the organic polymer uniformly distributed in the composite anode is partially carbonized through instantaneous large current, and the obtained organic polymer anode containing partial carbonization can resist higher voltage, so that the problem of polymer instability under high voltage is effectively solved. When the electrolyte is applied to a solid electrolyte, the electrolyte can bear higher voltage, the problem of interface contact performance of a positive electrode/the solid electrolyte in a solid battery is solved, and the safety and the cycle stability of the solid battery are effectively improved; the whole operation process of the invention is simple and efficient, and the flow is reasonable.

Description

Large-current in-situ carbonization method for solid electrolyte anode
Technical Field
The invention relates to the technical field of anode materials, in particular to a high-current in-situ carbonization method for a solid electrolyte anode.
Background
The existing commercial lithium ion battery is mostly organic liquid electrolyte, and a series of safety problems such as fire, explosion and the like are easily caused due to the inflammable characteristic, and the energy and power density of the existing commercial lithium ion battery can not meet the requirements of the current society, and some high-power energy storage devices such as electric vehicles, smart grids and the like.
It is therefore routine to develop a next generation of solid-state batteries with high specific energy and high safety, but the small effective contact area due to the solid-state electrolyte and electrode solid-state contact generally results in high interfacial resistance, which in turn limits the solid-state battery energy and power density. The current solution to the solid electrolyte positive electrode cross section is as follows:
1. regarding the problem of interface contact between the solid electrolyte and the anode, since the composite electrolyte membrane of the polymer matrix has excellent flexibility and processability, the ion conductivity of the LLZO/anode interface and the solid electrolyte can be effectively improved by adopting the common polyethylene oxide (PEO) as the polymer matrix, adding lithium salts in different proportions and using inorganic fillers with different LLZO particle sizes.
The ion conduction in the LLZO-PEO composite electrolyte is different from a grain-grain boundary mode of the LLZO ceramic electrolyte and a high molecular chain segment motion conduction mode of the polymer electrolyte, a space charge layer exists at a contact interface of the LLZO and the PEO, and lithium ions can be rapidly transmitted through the space charge layer at the LLZO/PEO interface.
2. The film electrode is constructed by using a film deposition technology, the positive electrode layer is directly grown on one side of the solid electrolyte by using the film deposition technology such as PLD and magnetron sputtering technology, and the composite metal lithium negative electrode is used on the other side, so that the positive electrode layer and the solid electrolyte interface in the battery are in good contact.
3. The contact effect between the positive electrode and the solid electrolyte interface is improved by introducing the polymer interface layer, namely introducing the polymer interface layer, and the solid electrolyte and the positive electrode can be well contacted by utilizing the flexibility characteristic of the prepared gel polymer electrolyte and inserting the gel polymer electrolyte as an intermediate layer between the positive electrode and the solid electrolyte.
4. The anode material is directly coated on the solid electrolyte and is sintered at high temperature [6,7], a modification layer can be generated on the interface of the solid electrolyte by using an in-situ method, the anode material is directly coated on the surface of the LLZO solid electrolyte and is co-sintered at the gradient temperature to prepare the composite anode, and the battery made by matching the lithium metal cathode can obviously improve the specific energy of discharge and the coulomb efficiency.
First, however, a commonly used organic polymer such as polyethylene oxide PEO is used as a polymer matrix, and LLZO is added to construct a LLZO-PEO composite electrolyte to solve the problems of low ionic conductivity and interface. However, the LLZO nanoparticles are limited in their mass production and further commercialization to some extent because of their high surface energy, large difference in surface energy from the polymer matrix PEO, serious agglomeration between particles, and improved interfacial contact between particles and polymer molecules.
Secondly, the positive electrode is constructed by adopting the thin film deposition technology, but the method has the disadvantages that high-temperature heat treatment is required when the electrode is prepared by the method, so that the activities of elements of an electrolyte and a positive electrode material are enhanced, interface reaction is easy to cause, and higher interface resistance is formed, and the positive electrode layer of the all-solid-state lithium ion battery prepared by the thin film deposition has lower active substance content, so that the capacity of the battery is lower, and the cost required by adopting the PLD and the magnetron sputtering technology is relatively higher, so that the large-scale production and further commercial application are difficult.
Third, the introduction of a polymer interfacial layer, while improving the contact between the positive electrode and the solid electrolyte, has yet to be explored because the introduction of additional intermediate layers has an unknown effect on the cycle life and safety performance of the battery.
Fourthly, the electronic conductivity of the composite anode prepared by the co-sintering method is poor, and the coating thickness before sintering is not easy to control, so that the thickness of the composite anode is limited, the energy density of the battery is reduced, and after the composite anode is cycled for a long time, the volume expansion of the anode material may cause a series of safety problems such as electrode expansion and pulverization.
Therefore, it is necessary to find an effective optimization method for improving the interface between the solid-state battery and the positive and negative electrodes, and simultaneously ensuring the stability of the electrode itself.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a high-current in-situ carbonization method for a solid electrolyte anode, which effectively solves the problem of instability of a composite electrode containing a polymer under high voltage, and simultaneously can effectively solve the problems of poor contact of a solid-solid interface of an electrode/electrolyte and capacity attenuation of a battery caused by lithium loss in a circulation process due to insufficient contact of the solid-solid interface.
The technical scheme of the invention is as follows: a high-current in-situ carbonization method for a solid electrolyte anode specifically comprises the following steps,
s1), polishing and grinding the solid electrolyte matrix;
s2) mixing an organic polymer and a certain amount of positive active material raw materials to obtain an organic composite positive raw material, and uniformly mixing the mixed organic composite positive raw material by magnetic stirring;
s3), transferring the uniformly mixed organic composite anode raw material into a glove box filled with Ar gas atmosphere;
s4), uniformly coating the uniformly mixed organic composite anode raw material on the surface of the polished solid electrolyte in a glove box;
s5), and after the coating is uniform, applying a momentary large current to partially carbonize the organic polymer coated on the surface of the solid electrolyte.
Further, in step S1), the solid electrolyte is a garnet-type inorganic solid electrolyte.
Further, in step S2), the mass fraction of the organic polymer added is 5%.
Further, in step S2), the organic polymer is one or more of PEO, PAN, PVDF-HFP.
Further, in step S2), the positive electrode active material is a mixture of PVDF: super P ═ 1:8: 1.
Further, in step S2), the magnetic stirring speed is as follows: the stirring speed is as follows: the stirring time at 200r/min is as follows: 2-3 h.
Further, in step S4), the step of coating the organic composite cathode raw material on the surface of the solid electrolyte is specifically as follows: the mixed slurry was placed on a solid electrolyte and coated with a spatula to a thickness of 30 μm.
Further, in step S4), the instantaneous large current is introduced to 8-10mAcm -2 。
The invention has the beneficial effects that:
1. according to the invention, the organic polymer and the positive active material with a certain proportion are mixed and coated on the surface of the solid electrolyte, and the organic polymer uniformly distributed in the composite positive electrode is partially carbonized through instantaneous large current, so that the obtained organic polymer positive electrode containing partial carbonization can resist higher voltage, and the problem of polymer instability under high voltage is effectively solved.
2. According to the invention, the optimization effect on the solid electrolyte | electrode interface can be further improved, so that the composite anode mixed with the organic polymer can bear higher voltage when being applied to the solid electrolyte, the problem of interface contact performance of the anode/the solid electrolyte in the solid battery is solved, and the safety and the cycle stability of the solid battery are effectively improved;
3. according to the invention, as the organic polymer is uniformly distributed in the composite anode, after the organic polymer in the composite anode is partially carbonized in situ, the obtained partially carbonized organic polymer-containing composite anode can withstand higher voltage.
4. The invention can effectively solve the problem of polymer instability under high voltage, and improve the problems of unstable solid-solid contact in the solid-state battery and capacity loss caused by poor contact in the circulating process;
5. the whole operation process of the invention is simple and efficient, and the flow is reasonable.
Drawings
FIG. 1 is a flow chart of an embodiment of the present invention.
Detailed Description
The following further describes embodiments of the present invention with reference to the accompanying drawings:
example 1
As shown in fig. 1, the present embodiment provides a high current in-situ carbonization method for solid electrolyte positive electrode, specifically comprising the following steps,
s1), polishing and grinding the solid electrolyte matrix to remove a series of impurities such as lithium carbonate and lithium hydroxide generated on the surface during high-temperature sintering or air contact, wherein the solid electrolyte used in this embodiment is garnet-type inorganic solid electrolyte;
s2) mixing an organic polymer and a certain amount of positive active material raw materials to obtain an organic composite positive raw material, and uniformly mixing the mixed organic composite positive raw material by magnetic stirring; in this embodiment, the organic polymer is one or a mixture of PEO, PAN, and PVDF-HFP, and the positive active material is PVDF: super P ═ 1:8: 1. The amount of the added positive active substance raw material is 5 percent of the mass of the mixed material, the magnetic stirring condition is 200r/min, and the stirring is carried out for 2 hours
S3), transferring the uniformly mixed organic composite anode raw material into a glove box filled with Ar gas atmosphere;
s4), uniformly coating the uniformly mixed organic composite anode raw material on the surface of the polished solid electrolyte in a glove box, wherein the coating thickness is 30 mu m;
s5), after the coating is uniform, the instantaneous high current is introduced to carbonize the organic polymer part coated on the surface of the solid electrolyte, wherein the introduced instantaneous high current is 8mAcm -2 。
Example 2
The embodiment provides a high-current in-situ carbonization method for a solid electrolyte anode, which specifically comprises the following steps,
s1), polishing and grinding the solid electrolyte matrix to remove a series of impurities such as lithium carbonate and lithium hydroxide generated on the surface during high-temperature sintering or air contact, wherein the solid electrolyte used in this embodiment is garnet-type inorganic solid electrolyte;
s2) mixing an organic polymer and a certain amount of positive active material raw materials to obtain an organic composite positive raw material, and uniformly mixing the mixed organic composite positive raw material by magnetic stirring; in this embodiment, the organic polymer is one or a mixture of PEO, PAN, and PVDF-HFP, and the positive active material is PVDF: super P ═ 1:8: 1. The magnetic stirring conditions are as follows: stirring for 2.5h at 200 r/min.
S3), transferring the uniformly mixed organic composite anode raw material into a glove box filled with Ar gas atmosphere;
s4), uniformly coating the uniformly mixed organic composite anode raw material on the surface of the polished solid electrolyte in a glove box, wherein the coating thickness is 30 mu m, and the specific coating process is as follows; the mixed slurry was placed on a solid electrolyte and coated with a spatula.
S5), after the coating is uniform, introducing instantaneous large current to partially carbonize the organic polymer coated on the surface of the solid electrolyte, wherein the introduced instantaneous large current is 9mAcm -2 。
Example 3
The embodiment provides a high-current in-situ carbonization method for a solid electrolyte anode, which specifically comprises the following steps,
s1), polishing and grinding the solid electrolyte matrix to remove a series of impurities such as lithium carbonate and lithium hydroxide generated on the surface during high-temperature sintering or air contact, wherein the solid electrolyte used in this embodiment is garnet-type inorganic solid electrolyte;
s2) mixing an organic polymer and a certain amount of positive active material raw materials to obtain an organic composite positive raw material, and uniformly mixing the mixed organic composite positive raw material by magnetic stirring; in this embodiment, the organic polymer is one or a mixture of PEO, PAN, and PVDF-HFP, and the positive active material is PVDF: super P ═ 1:8: 1. The magnetic stirring conditions are as follows: the stirring speed is as follows: the stirring time at 200r/min is as follows: 2-3 h.
S3), transferring the uniformly mixed organic composite anode raw material into a glove box filled with Ar gas atmosphere;
s4), uniformly coating the uniformly mixed organic composite cathode raw material on the surface of the polished solid electrolyte in a glove box, wherein the coating thickness is 30 mu m.
S5), after the coating is uniform, the instantaneous high current is introduced to carbonize the organic polymer part coated on the surface of the solid electrolyte, wherein the introduced instantaneous high current is 8.5mAcm -2 。
Example 4
The embodiment provides a high-current in-situ carbonization method for a solid electrolyte anode, which specifically comprises the following steps,
s1), polishing and grinding the solid electrolyte matrix to remove a series of impurities such as lithium carbonate and lithium hydroxide generated on the surface during high-temperature sintering or air contact, wherein the solid electrolyte used in this embodiment is garnet-type inorganic solid electrolyte;
s2) mixing an organic polymer and a certain amount of positive active material raw materials to obtain an organic composite positive raw material, and uniformly mixing the mixed organic composite positive raw material by magnetic stirring; in this embodiment, the organic polymer is one or a mixture of PEO, PAN, and PVDF-HFP, and the positive active material is PVDF: super P ═ 1:8: 1.
S3), transferring the uniformly mixed organic composite anode raw material into a glove box filled with Ar gas atmosphere;
s4), uniformly coating the uniformly mixed organic composite anode raw material on the surface of the polished solid electrolyte in a glove box, wherein the coating thickness is 30 mu m;
s5), after the coating is uniform, applying instantaneous high current to partially carbonize the organic polymer coated on the surface of the solid electrolyte, wherein the applied instantaneous high current is 10mAcm -2 。
Example 5
The embodiment provides a high-current in-situ carbonization method for a solid electrolyte anode, which specifically comprises the following steps,
s1), polishing and grinding the solid electrolyte matrix to remove a series of impurities such as lithium carbonate and lithium hydroxide generated on the surface during high-temperature sintering or air contact, wherein the solid electrolyte used in this embodiment is garnet-type inorganic solid electrolyte;
s2) mixing an organic polymer and a certain amount of positive active material raw materials to obtain an organic composite positive raw material, and uniformly mixing the mixed organic composite positive raw material by magnetic stirring; in this embodiment, the organic polymer is one or a mixture of PEO, PAN, and PVDF-HFP, and the positive active material is PVDF: super P ═ 1:8: 1.
S3), transferring the uniformly mixed organic composite anode raw material into a glove box filled with Ar gas atmosphere;
s4), uniformly coating the uniformly mixed organic composite anode raw material on the surface of the polished solid electrolyte in a glove box, wherein the coating thickness is 30 mu m;
s5), after the coating is uniform, applying instantaneous high current to partially carbonize the organic polymer coated on the surface of the solid electrolyte, wherein the applied instantaneous high current is 9.5mAcm -2 。
Example 6
The embodiment provides a high-current in-situ carbonization method for a solid electrolyte anode, which specifically comprises the following steps,
s1), polishing and grinding the solid electrolyte matrix to remove a series of impurities such as lithium carbonate and lithium hydroxide generated on the surface during high-temperature sintering or air contact, wherein the solid electrolyte used in this embodiment is garnet-type inorganic solid electrolyte;
s2) mixing an organic polymer and a certain amount of positive active material raw materials to obtain an organic composite positive raw material, and uniformly mixing the mixed organic composite positive raw material by magnetic stirring; in this embodiment, the organic polymer is one or a mixture of PEO, PAN, and PVDF-HFP, and the positive active material is PVDF: super P ═ 1:8: 1.
S3), transferring the uniformly mixed organic composite anode raw material into a glove box filled with Ar gas atmosphere;
s4), uniformly coating the uniformly mixed organic composite anode raw material on the surface of the polished solid electrolyte in a glove box, wherein the coating thickness is 30 mu m;
s5), after the coating is uniform, the instantaneous high current is introduced to carbonize the organic polymer part coated on the surface of the solid electrolyte, wherein the introduced instantaneous high current is 8.8mAcm -2 。
In the embodiment of the invention, the organic polymer and the positive active material raw material with a certain proportion are uniformly mixed and coated on the surface of the solid electrolyte, and then the organic polymer in the composite positive electrode is partially carbonized in situ by introducing instantaneous large current; because the organic polymer is uniformly distributed in the composite anode, after the organic polymer in the composite anode is partially carbonized in situ, the obtained partially carbonized organic polymer-containing composite anode can bear higher voltage. The problem of polymer instability under high voltage is effectively solved, and the problems of solid-solid contact instability in a solid-state battery and capacity loss caused by poor contact property in a circulating process are solved.
The foregoing embodiments and description have been presented only to illustrate the principles and preferred embodiments of the invention, and various changes and modifications may be made therein without departing from the spirit and scope of the invention as hereinafter claimed.

Claims (6)

1. A high-current in-situ carbonization method for a solid electrolyte anode is characterized by comprising the following steps of,
s1), polishing and grinding the solid electrolyte matrix;
s2) mixing an organic polymer and a certain amount of positive active material raw materials to obtain an organic composite positive raw material, and uniformly mixing the mixed organic composite positive raw material by magnetic stirring;
s3), transferring the uniformly mixed organic composite anode raw material into a glove box filled with Ar gas atmosphere;
s4), uniformly coating the uniformly mixed organic composite anode raw material on the surface of the polished solid electrolyte in a glove box;
s5), after the coating is uniform, the instantaneous high current is introduced to carbonize the organic polymer part coated on the surface of the solid electrolyte, wherein the introduced instantaneous high current is 8-10mA cm -2 。
2. A high current in-situ carbonization method for solid electrolyte positive electrodes as claimed in claim 1, characterized in that: in step S1), the solid electrolyte is a garnet-type inorganic solid electrolyte.
3. A high current in-situ carbonization method for solid electrolyte positive electrodes as claimed in claim 1, characterized in that: in step S2), the organic polymer is one or more of PEO, PAN, PVDF-HFP.
4. A high current in-situ carbonization method for solid electrolyte positive electrodes as claimed in claim 1, characterized in that: in step S2), the positive electrode active material is PVDF: super P ═ 1:8: 1.
5. A high current in-situ carbonization method for solid electrolyte positive electrodes as claimed in claim 1, characterized in that: in step S2), the magnetic stirring rate is: 200r/min, stirring time is as follows: 2-3 h.
6. A high current in-situ carbonization method for solid electrolyte positive electrodes as claimed in claim 1, characterized in that: in step S4), the specific manner of coating the organic composite positive electrode raw material on the surface of the solid electrolyte is as follows: the mixed slurry was placed on a solid electrolyte and coated with a spatula to a thickness of 30 μm.
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