CN117832377B - In-situ doping preparation method of all-solid-state thin-film battery electrode - Google Patents
In-situ doping preparation method of all-solid-state thin-film battery electrode Download PDFInfo
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- 239000010409 thin film Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 16
- 239000000463 material Substances 0.000 claims abstract description 19
- 238000004544 sputter deposition Methods 0.000 claims abstract description 18
- 239000007772 electrode material Substances 0.000 claims abstract description 10
- 239000010408 film Substances 0.000 claims abstract description 7
- 239000000758 substrate Substances 0.000 claims abstract description 7
- 238000002425 crystallisation Methods 0.000 claims abstract description 3
- 230000008025 crystallization Effects 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 8
- 238000000151 deposition Methods 0.000 claims description 5
- 230000008021 deposition Effects 0.000 claims description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Chemical compound O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 claims description 4
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 3
- 229910001367 Li3V2(PO4)3 Inorganic materials 0.000 claims description 2
- 229910032387 LiCoO2 Inorganic materials 0.000 claims description 2
- 229910011279 LiCoPO4 Inorganic materials 0.000 claims description 2
- 229910011275 LiCoPO4F Inorganic materials 0.000 claims description 2
- 229910016120 LiMn1.5Ni0.5O2 Inorganic materials 0.000 claims description 2
- 229910013084 LiNiPO4 Inorganic materials 0.000 claims description 2
- 229910052768 actinide Inorganic materials 0.000 claims description 2
- 150000001255 actinides Chemical class 0.000 claims description 2
- 229910052747 lanthanoid Inorganic materials 0.000 claims description 2
- 150000002602 lanthanoids Chemical class 0.000 claims description 2
- 229910001386 lithium phosphate Inorganic materials 0.000 claims description 2
- 238000001451 molecular beam epitaxy Methods 0.000 claims description 2
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 239000002131 composite material Substances 0.000 abstract description 3
- 238000005289 physical deposition Methods 0.000 abstract description 3
- 239000013077 target material Substances 0.000 abstract description 3
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 29
- 229910013733 LiCo Inorganic materials 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 16
- 229910016289 MxO2 Inorganic materials 0.000 description 15
- 239000007774 positive electrode material Substances 0.000 description 14
- 238000012360 testing method Methods 0.000 description 14
- 239000010406 cathode material Substances 0.000 description 13
- 238000000137 annealing Methods 0.000 description 10
- 229910012305 LiPON Inorganic materials 0.000 description 8
- 238000001816 cooling Methods 0.000 description 8
- 239000010405 anode material Substances 0.000 description 7
- 229910012820 LiCoO Inorganic materials 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000009792 diffusion process Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 230000008859 change Effects 0.000 description 3
- 230000001351 cycling effect Effects 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 230000002441 reversible effect Effects 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000010354 integration Effects 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 206010063385 Intellectualisation Diseases 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052956 cinnabar Inorganic materials 0.000 description 1
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 238000007709 nanocrystallization Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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Abstract
The invention discloses an in-situ doping preparation method of an electrode of an all-solid-state thin film battery, which comprises the following steps: step 1, sputtering a doped material layer with the thickness of 1 nm-20 mu m on a current collector in advance; and 2, growing a doping film electrode material on the surface of the doping layer in the step 1, and carrying out doping crystallization at the substrate temperature of 400-900 ℃ under the pressure of 1X 10 ‑1～1×10‑4 mbar. The invention solves the problems that the preparation of the film type all-solid-state battery is limited by a physical deposition mode of stacking layers, and the preparation of the composite target material and the multi-target co-sputtering doping only need to meet the severe preparation conditions and the high target manufacturing cost, thereby being unfavorable for mass production.
Description
Technical Field
The invention belongs to the technical field of solid-state batteries of new energy devices, and particularly relates to an in-situ doping preparation method of an electrode of an all-solid-state thin-film battery.
Background
The commercialized application of the all-solid-state film battery solves the energy storage problem of the miniature electric equipment to a great extent. Along with the continuous improvement of the requirements of intellectualization, microminiaturization and integration, a thin film type all-solid-state lithium battery with high energy density, stable electrochemical performance, safety and low cost becomes a research hot spot at the present stage. The positive electrode material serving as a lithium source donor not only provides lithium ions migrating during the cycle, but also meets the requirement of interfacial layer growth. In addition, when Li + comes out to reach the threshold, irreversible structural phase change, lattice distortion and release of lattice oxygen gradually aggravate structural instability, causing serious cycle life decay.
Doping is a common and effective modification method. Through element doping, elements with different valence states or ion radiuses can be combined together, so that the electronic structure of the material is optimized along with the doping elements, and various properties of the material are improved. Considering that the preparation of the film type all-solid-state battery is limited by the physical deposition mode of layer-by-layer stacking, the preparation of the composite target material and the multi-target co-sputtering doping are required to meet the severe preparation conditions and the high target preparation cost, so that the mass production is not facilitated. However, the requisite high temperature annealing process is a prerequisite for obtaining a well-crystallized electrode material, and lengthy external annealing steps can cause surface contamination of the material. Inert byproducts such as Li 2O、CoO、Co3O4 formed on the surface of commercial LiCoO 2 thin film electrodes, amorphous LiCoO 2 growth layers and intra-crystalline cracks, cause an increase in interface resistance after cycling, ion diffusion path blockage and complex phase change processes. Therefore, the method can simultaneously meet the doping of low temperature and high crystallinity, alleviate the change of lattice stress, and improve the voltage hysteresis between interfaces to obtain the electrode material with high energy density, which is a technical problem to be overcome in the high integration link of energy sources/devices.
Disclosure of Invention
The invention aims to provide an in-situ doping preparation method of an electrode of an all-solid-state thin-film battery, which solves the problems that the preparation of the existing thin-film all-solid-state battery is limited by a physical deposition mode of stacking layers, and the preparation of a composite target material and multi-target co-sputtering doping are unfavorable for mass production because severe preparation conditions and high target preparation cost are required.
In order to achieve the above purpose, the technical scheme of the scheme is as follows: an in-situ doping preparation method of an all-solid-state thin film battery electrode comprises the following steps:
And step 1, sputtering a doped material layer with the thickness of 1 nm-20 mu m on the current collector in advance.
And 2, growing a doping film electrode material on the surface of the doping material layer in the step 1, and carrying out doping crystallization at the substrate temperature of 400-900 ℃ under the pressure of 1X 10 -1mbar～1×10-4 mbar.
Preferably, the dopable thin film electrode material includes any one or more of ：VO2、V2O5、TiO2、Nb2O5、LiCoO2、Li3PO4、LiCoPO4、LiCoPO4F、LiNiPO4、Li3V2(PO4)3、LiMn1.5Ni0.5O2 and Li 2TMSiO4 (tm= Fe, mn, co, ni).
Preferably, the doped material layer comprises: sc, ti, V, cr, mn, fe, cu, zn, co, ni, K, na, sn, ag, au, al, ta, W (Sc, ti, V, cr, mn, fe, cu, zn, co, ni, K, na, sn, ag, au, al, ta, W) any one or more of the lanthanides and actinides.
Preferably, the thin film processing method in the preparation process of the thin film electrode doped material layer comprises the following steps: any one or more of magnetron sputtering, pulsed laser beam deposition, molecular beam epitaxy.
The beneficial effects of the invention are as follows: the invention provides an in-situ doping preparation method based on a film electrode, which ensures that the anode material has obvious preferential growth and intragranular defects in the doping process, avoids stress aggregation and crack occurrence in a bulk phase, increases ion diffusion kinetics and structural stability, and comprehensively improves the electrochemical performance of the electrode material.
Drawings
FIG. 1 is a schematic illustration of atomic diffusion of a doped layer in a thin film electrode prepared based on in situ doping according to the present invention;
Fig. 2 is an SEM image of LiCo 1-xTixO2 positive electrode material prepared in example 2 and undoped LiCoO 2 positive electrode;
FIG. 3 is a graph of the long cycle performance of LiCo 1-xTixO2 positive electrode material prepared in example 2 versus undoped LiCo O 2 positive electrode at 0.3C rate at room temperature;
fig. 4 is a charge-discharge graph of LiCo 1-xTixO2 positive electrode material prepared in example 2 and undoped LiCoO 2 positive electrode at different circles;
Fig. 5 is an EIS diagram of the LiCo 1-xTixO2 positive electrode material prepared in example 2 and undoped LiCo 2 before and after positive cycling.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Fig. 1 is a schematic view of atomic diffusion of a doped layer in an in-situ doping-based preparation of a thin film electrode according to the present invention, and an in-situ doping preparation method of an all-solid-state thin film battery electrode according to the present invention is implemented by the following examples.
Example 1
The doped material layer is pre-sputtered on the surface of the current collector in a magnetron sputtering mode, the thickness of the doped material layer is about 1 mu m, the sputtering condition is 1 multiplied by 10 -1 mbar pressure, the substrate temperature is 800 ℃, the atmosphere is Ar/O 2 mixed gas (the flow is kept at 80/20 sccm), and the annealing time is 10min. And then carrying out in-situ sputtering on the anode LiCoO 2 to be modified under the above conditions, taking out after the sputtering is finished and cooling, and preparing the doped anode material LiCoO 1-xTixO2 (x represents doping amount).
Comparative example 1
LiCoO 2 was placed under a pressure of 1X 10 -1 mbar at an annealing temperature of 800℃in an atmosphere of Ar/O 2 mixture (flow rate maintained at 80/20 sccm) for a reaction time of 10 minutes, and after cooling, the resulting undoped LiCoO 2 positive electrode material was obtained.
The doped cathode material LiCo 1-xTixO2 (x represents doping amount) prepared in example 1 and the undoped LiCoO 2 cathode material prepared in comparative example 1 were assembled with LiPON electrolyte and Li negative electrode, respectively, into an all-solid-state thin film battery.
Test experiment
The example 1 doped positive electrode material LiCo 1-xTixO2 (x represents doping amount) and the comparative example 1 undoped LiCoO 2 positive electrode material were assembled into an all-solid-state thin film battery for constant current charge and discharge test, the voltage range of the test was 3-4.6V, the current density was 0.3C, the discharge temperature was 25 ℃, and the model of the test instrument was blue CT2001A (Wuhan Jinno electronics Co.). The specific discharge capacities of the doped LiCoO 1-xMxO2 (x represents the doping amount) obtained in example 1 and the undoped LiCoO 2 cathode material of comparative example 1 after 100 cycles were 63 μah cm -2μm-1 and 49 μah cm -2μm-1, respectively.
Example 2
The doped material layer is pre-sputtered on the surface of the current collector by adopting a pulse laser deposition mode, the thickness of the doped material layer is about 20nm, the sputtering condition is 1 multiplied by 10 -4 mbar pressure, the substrate temperature is 600 ℃, the atmosphere is Ar/O 2 mixed gas (the flow is kept at 80/20 sccm), and the annealing time is 20min. And then carrying out in-situ sputtering on the anode LiCoO 2 to be modified under the above conditions, and taking out after the sputtering is finished and cooling to obtain the preparation.
Comparative example 2
LiCoO 2 was placed under a pressure of 1X 10 -4 mbar at an annealing temperature of 600℃in an atmosphere of Ar/O 2 mixture (flow rate maintained at 80/20 sccm) for a reaction time of 20 minutes, and after cooling, the resulting undoped LiCoO 2 positive electrode material was obtained.
Test experiment
The doped cathode materials LiCo 1-xMxO2 (x represents doping amount) prepared in example 2 and the undoped LiCoO 2 cathode material of comparative example 2 were assembled with LiPON electrolyte and Li negative electrode, respectively, into an all-solid-state thin film battery.
The specific discharge capacities of the above example 2 doped LiCo 1-xMxO2 (x represents the doping amount) and comparative example 2 undoped LiCoO 2 cathode materials after 100 cycles were 65 and 50 μah cm -2μm-1, respectively.
The doped layer prepared in example 2 was formed into an all-solid-state thin-film battery LiCoO 1-xMxO2 (/ LiPON/Li (x represents doping amount) and the undoped LiCoO 2 positive electrode material prepared in comparative example 2 was formed into an all-solid-state thin-film battery LiCoO 2/LiPON/Li, and electrochemical performance test was performed with a test instrument model of a blue charge/discharge tester.
As shown in fig. 3, the modified all-solid-state thin film battery was placed in a voltage interval of 3-4.6V and was charge-discharge cycled 100 times at a current density of 0.3C, and as a result, it was shown that the doped LiCoO 2 had a higher discharge capacity and capacity retention rate.
As shown in fig. 2, SEM images of the modified LiCo 1-xMxO2 (x represents doping amount) show that obvious nanocrystallization phenomenon appears on the surface, which is beneficial to the increase of active sites; CV test results show that the electrode has smaller polarized internal resistance, voltage hysteresis and reversible charge/discharge platform, and EIS further proves that doping is helpful for reducing the internal resistance and charge transfer resistance of the battery before and after circulation, and faster electrochemical kinetics process is shown, so that the electrode has good high-voltage reversible cycle life.
Example 3
The doped material layer is pre-sputtered on the surface of the current collector by adopting a pulse laser deposition mode, the thickness of the doped material layer is about 30nm, the sputtering condition is 1 multiplied by 10 -3 mbar pressure, the substrate temperature is 500 ℃, the atmosphere is Ar/O 2 mixed gas (the flow is kept at 80/20 sccm), and the annealing time is 20min. And then carrying out in-situ sputtering on the LiCoO 2 of the anode to be modified under the above conditions, and taking out after the sputtering is finished and cooling, thus obtaining the prepared doped anode material LiCoO 1-xMxO2 (x represents doping amount).
Comparative example 3
LiCoO 2 was placed under a pressure of 1X 10 -3 mbar at an annealing temperature of 500℃in an atmosphere of Ar/O 2 mixture (flow rate maintained at 80/20 sccm) for a reaction time of 20 minutes, and after cooling, the resulting undoped LiCoO 2 positive electrode material was obtained.
Test experiment
The doped cathode materials LiCo 1-xMxO2 (x represents doping amount) prepared in example 3 and the undoped LiCoO 2 cathode material of comparative example 3 were assembled with LiPON electrolyte and Li negative electrode, respectively, into an all-solid-state thin film battery. The specific discharge capacities of the example 3 doped positive electrode material LiCo 1-xMxO2 (x represents the doping amount) and the comparative example 3 undoped LiCoO 2 positive electrode material after 100 cycles were 62 μah cm -2μm-1 and 47 μah cm -2μm-1, respectively.
The electrochemical performance test was performed by combining the anode material LiCo 1-xMxO2 (x represents doping amount) of example 3 into an all-solid-state thin-film battery LiCo 1- xMxO2/LiPON/Li and the anode material LiCo 2 of comparative example 3 into an all-solid-state thin-film battery LiCo 2/LiPON/Li, and the model of the test instrument was a blue charge/discharge tester.
The test results are shown in (a) and (b) of fig. 4, and the modified electrode shows smaller polarization internal resistance, voltage hysteresis and reversible charge/discharge platform.
Example 4
The doped material layer is pre-sputtered on the surface of the current collector by adopting a pulse laser deposition mode, the thickness of the doped material layer is about 20nm, the sputtering condition is 1 multiplied by 10 -2 mbar pressure, the substrate temperature is 400 ℃, the atmosphere is Ar/O 2 mixed gas (the flow is kept at 80/20 sccm), and the annealing time is 30min. And then in-situ sputtering the to-be-modified anode LiCoO 2 under the above conditions, cooling after the sputtering is finished, and taking out to obtain the prepared doped anode material LiCoO 1-xMxO2 (x represents doping amount) and undoped anode material LiCoO 2.
Comparative example 4
LiCoO 2 was placed under a pressure of 1X 10 -2 mbar at an annealing temperature of 400℃in an atmosphere of Ar/O 2 mixture (flow rate maintained at 80/20 sccm) for a reaction time of 30 minutes, and after cooling, the resulting undoped LiCoO 2 positive electrode material was obtained.
Test experiment
The doped cathode material LiCo 1-xMxO2 (x represents doping amount) prepared in example 4 and the undoped LiCoO 2 cathode material in comparative example 4 were respectively discharged to specific capacities of 59 μah cm -2μm-1 and 45 μah cm -2μm-1 after 100 cycles of the doped cathode material LiCo 1-xMxO2 (x represents doping amount) in example 4 and the undoped LiCoO 2 cathode material in comparative example 4, respectively.
The electrode material of the doped layer of example 4 and the electrode material of the undoped layer of comparative example 4 are respectively combined into an all-solid-state thin-film battery LiCo 1-xMxO2/LiPON/Li (x represents doping amount), and an electrochemical impedance test is performed, and the model of a test instrument is cinnabar potentiostat.
The test results are shown in fig. 5 (a) and (b), and the results show that the doped layers help reduce the internal resistance and the charge transfer resistance of the cell before and after cycling, and represent a faster electrochemical kinetics process.
The specific discharge capacity after 100 cycles of the doped cathode material LiCo 1-xMxO2 (x represents the doping amount) prepared in example 2 was found to be the best 64. Mu. Ah cm -2μm-1 by examples 1-4.
While the present invention has been described in detail through the foregoing description of the preferred embodiment, it should be understood that the foregoing description is not to be considered as limiting the invention. Many modifications and substitutions of the present invention will become apparent to those of ordinary skill in the art upon reading the foregoing. Accordingly, the scope of the invention should be limited only by the attached claims.
Claims (2)
1. The in-situ doping preparation method of the all-solid-state thin film battery electrode is characterized by comprising the following steps of:
Step 1, sputtering a doped material layer with the thickness of 1 nm-20 mu m on a current collector in advance;
step 2, growing a doping film electrode material on the surface of the doping material layer in the step 1, and carrying out doping crystallization at the substrate temperature of 400-900 ℃ under the pressure of 1X 10 -1mbar~1×10-4 mbar;
The doped material layer includes: sc, ti, V, cr, mn, fe, cu, zn, co, ni, K, na, sn, ag, au, al, ta, W, any one or more of the lanthanides and actinides;
The dopable thin film electrode material includes any one or more of ：VO2、V2O5、TiO2、Nb2O5、LiCoO2、Li3PO4、LiCoPO4、LiCoPO4F、LiNiPO4、Li3V2(PO4)3、LiMn1.5Ni0.5O2 and Li 2TMSiO4; tm= Fe, mn, co, ni.
2. The method for preparing an all-solid-state thin-film battery electrode by in-situ doping according to claim 1, wherein the thin-film treatment method in the preparation process of the all-solid-state thin-film battery electrode comprises the following steps: any one or more of magnetron sputtering, pulsed laser beam deposition, molecular beam epitaxy.
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