CN116845333A - All-solid-state thin-film lithium ion battery and preparation method thereof - Google Patents
All-solid-state thin-film lithium ion battery and preparation method thereof Download PDFInfo
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- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 41
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- 238000002360 preparation method Methods 0.000 title abstract description 15
- 239000003792 electrolyte Substances 0.000 claims abstract description 122
- 229910012305 LiPON Inorganic materials 0.000 claims abstract description 47
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 43
- 238000001755 magnetron sputter deposition Methods 0.000 claims abstract description 42
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 39
- 238000005245 sintering Methods 0.000 claims abstract description 29
- 238000012986 modification Methods 0.000 claims abstract description 17
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- 239000013077 target material Substances 0.000 claims abstract description 13
- 238000000151 deposition Methods 0.000 claims abstract description 11
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- 238000010276 construction Methods 0.000 claims abstract description 4
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 claims abstract description 4
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000007774 positive electrode material Substances 0.000 claims abstract description 4
- 238000004544 sputter deposition Methods 0.000 claims description 136
- 238000000034 method Methods 0.000 claims description 19
- 230000001105 regulatory effect Effects 0.000 claims description 14
- 238000000280 densification Methods 0.000 claims description 11
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 10
- 239000010949 copper Substances 0.000 claims description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- 238000004321 preservation Methods 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
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- 229910009511 Li1.5Al0.5Ge1.5(PO4)3 Inorganic materials 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 2
- 229910005793 GeO 2 Inorganic materials 0.000 claims description 2
- 229910018068 Li 2 O Inorganic materials 0.000 claims description 2
- 229910052738 indium Inorganic materials 0.000 claims description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 2
- 238000003475 lamination Methods 0.000 claims description 2
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- 239000007784 solid electrolyte Substances 0.000 abstract description 22
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 210000004027 cell Anatomy 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 238000005520 cutting process Methods 0.000 description 6
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- 150000002500 ions Chemical class 0.000 description 4
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- PAHNBNDPQWLRQX-UHFFFAOYSA-N [N].[O].[P].[Li] Chemical compound [N].[O].[P].[Li] PAHNBNDPQWLRQX-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 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
- H01M10/052—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
- H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
- H01M10/0562—Solid materials
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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- Chemical Kinetics & Catalysis (AREA)
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- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
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- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
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Abstract
The invention discloses an all-solid-state film type lithium ion battery and a preparation method thereof, wherein the lithium ion battery consists of a positive electrode, a LAGP electrolyte compact layer, a LAGP-LiPON electrolyte gradient buffer layer, li 3 The N interface modification layer and the negative electrode are assembled in sequence; the positive electrode material is lithium cobalt oxide or lithium iron phosphate; the negative electrode is lithium metal; by Li 1+x Al x Ge 2‑x (PO 4 ) 3 Performing magnetron sputtering on the target material, and then placing the target material in a muffle furnace for sintering treatment to prepare a LAGP electrolyte compact layer; depositing a LAGP-LiPON electrolyte gradient buffer layer on the surface of the LAGP electrolyte compact layer; construction of Li on the negative lithium electrode side by in-situ chemical reaction of LiPON and molten lithium 3 An N interface modification layer; with lithium metalThe cathode and the anode are laminated and assembled into an all-solid-state thin film type lithium ion battery; the invention solves the problems of porosity and interface existing in the traditional sintering technology and magnetron sputtering technology by developing the integrated electrolyte based on the gradient solid electrolyte buffer layer and the negative electrode side interface modification layer.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to an all-solid-state thin-film lithium ion battery and a preparation method thereof.
Background
In recent years, in order to meet the power supply requirements of microchips, microelectromechanical systems, micro memories and the like in the low energy field, all-solid-state thin-film lithium ion batteries gradually become an important direction of battery microminiaturization technology and industry development, and magnetron sputtering technology is a technical foundation for realizing all-solid-state thin-film lithium ion batteries. Compared with the traditional liquid electrolyte-based lithium ion battery, the lithium ion battery adopting the solid electrolyte has the advantages that the runaway reaction caused by inflammable material components in the battery material is avoided, and the problem of fire or explosion of a new energy automobile is hopefully solved.
For lithium ion solid electrolyte, the inorganic solid electrolyte has the advantages of high temperature resistance, high safety, wide electrochemical window and the like, and mainly comprises perovskite type, NASICON type, LISICON type, li 3 N and glassy solid electrolytes, and the like. Among them, liPON (lithium phosphorus oxygen nitrogen) electrolyte is an amorphous electrolyte, which is a common electrolyte for thin film type lithium ion batteries, but is low in ion conductivity (10 -6 -10 -8 S/cm) has limited the further development of thin film solid state lithium ion batteries.
Crystalline electrolytes generally have a relatively high ionic conductivity and lithium ions are transported through lithium vacancies and lithium interstitial transitions in the crystal structure. Research on crystalline electrolytes has been mainly focused on electrolytes having LISICON structures, NASICON structures, perovskite structures, inverse perovskite structures, and garnet structures. NASICON type Li 1.5 Al 0.5 Ge 1.5 (PO 4 ) 3 The (LAGP) solid electrolyte has stable structure, wide working temperature range (-70-500 ℃), and electrochemical propertyThe learning window is wide>4V), high ion conductivity (10) -4 -10 -3 S/cm), good air stability, and the like. Specifically, by AlO 6 Octahedron and PO 4 The three-dimensional structure composed of tetrahedral co-vertices provides rich Li + And (5) migrating the channel. However, LAGP has a higher porosity during conventional sintering, resulting in lower ionic conductivity. Likewise, densification of LAGP tends to require higher temperatures and longer soak times, making it more difficult to reduce electrolyte thickness to below 200 microns, ultimately reducing electrolyte conductivity.
The magnetron sputtering technology can realize the thinning of the inorganic solid electrolyte, thereby improving the conductivity of the electrolyte, reducing the interface impedance and further realizing the manufacturing of the all-solid-state thin-film battery. However, the electrolyte prepared by magnetron sputtering may have pinholes and cracks, and is extremely easy to induce self-discharge to cause contact between positive and negative electrodes so as to cause short circuit, so that the electrolyte needs to meet the requirements of compactness, controllable thickness, high ion conductivity and the like.
Disclosure of Invention
The invention aims to provide an all-solid-state thin-film lithium ion battery and a preparation method thereof, and solves the problems of porosity and interfaces existing in the traditional sintering technology and magnetron sputtering technology by developing an integrated electrolyte based on a gradient solid electrolyte buffer layer and a negative electrode side interface modification layer.
In order to achieve the above purpose, the following technical scheme is adopted:
an all-solid-state film type lithium ion battery is composed of positive electrode, LAGP electrolyte compact layer, LAGP-LiPON electrolyte gradient buffer layer, li 3 The N interface modification layer and the negative electrode are assembled in sequence; the positive electrode material is lithium cobalt oxide or lithium iron phosphate; the negative electrode is lithium metal.
According to the scheme, the thickness of the LAGP electrolyte compact layer is 0.4-2 mu m; the thickness of the gradient LAGP-LiPON electrolyte gradient buffer layer is 200-400 nm; the Li is 3 The thickness of the N interface modification layer is 5-20 nm.
The preparation method of the all-solid-state thin-film lithium ion battery comprises the following steps:
1) By Li 1+x Al x Ge 2-x (PO 4 ) 3 Performing magnetron sputtering on the target material, and then placing the target material in a muffle furnace for sintering treatment to prepare a LAGP electrolyte compact layer;
2) Depositing a LAGP-LiPON electrolyte gradient buffer layer on the surface of the LAGP electrolyte compact layer;
3) Construction of Li on the negative lithium electrode side by in-situ chemical reaction of LiPON and molten lithium 3 An N interface modification layer;
4) And the lithium ion battery is assembled with a metal lithium anode and a metal lithium cathode in a lamination way to form an all-solid-state thin-film lithium ion battery.
According to the scheme, the LAGP solid electrolyte in the step 1 is a NICSION type electrolyte, in particular Li 1.5 Al 0.5 Ge 1.5 (PO 4 ) 3 。
According to the scheme, in the step 1, the LAGP solid electrolyte target material is Li 2 O、Al 2 O 3 、GeO 2 、P 2 O 5 The purity of the target material is 99.99%, the diameter of the target material is 50.8mm, and the thickness is 3.0mm; one side is tightly connected with copper targets with the same size and thickness of 1mm by metal indium;
the magnetron sputtering conditions include: the magnetron sputtering power is 40-160W, the magnetron sputtering temperature is 25-100 ℃, the target electrode distance is 6-10 cm, the magnetron sputtering pressure is 0.5-1 Pa, and the magnetron sputtering time is 1-24 h.
According to the scheme, the muffle furnace sintering treatment conditions in the step 1 comprise: the temperature rising rate is 2-10 ℃/min, the densification temperature is 750-950 ℃, and the heat preservation time is 3-8 h.
According to the above scheme, the sputtering step of the LAGP-LiPON electrolyte gradient buffer layer in the step 2 comprises the following steps: adopting a double-target sputtering mode, and respectively carrying out target LAGP and target Li under nitrogen atmosphere 3 PO 4 The gradient electrolyte buffer layer is fixed at two ends of a magnetron sputtering instrument chamber, the sputtering conditions are regulated and controlled by taking time as a control variable, and the gradient electrolyte buffer layer with high concentration of LAGP at the electrolyte side and high content of LiPON at the cathode side is constructed.
According to the scheme, the sputtering time of the LiPON is 0.5-3 h, the sputtering time of the LAGP is 1-5 h, and the sputtering time of the LiPON is ensured to be delayed by 0.5-1.5 h compared with the LAGP in the sputtering process.
According to the scheme, in-situ chemical reaction temperature of the LAGP-LiPON electrolyte buffer layer and molten lithium in the step 3 is 200-400 ℃; the reaction time is 1 min-3 min.
Compared with the prior art, the invention has the following beneficial effects:
the solid electrolyte used in the invention is solid electrolyte with high lithium ion conductivity, has a stable structure under air, and can realize room temperature or high temperature work.
The LAGP-LiPON electrolyte gradient buffer layer prepared by the invention adopts double-target material and controllable echelon sputtering, efficiently plays a synergistic effect, and effectively improves the (electrochemical) chemical stability of the electrolyte.
Li prepared on the negative electrode side according to the present invention 3 The N interface modification layer is Li formed based on in-situ chemical reaction of LiPON and molten lithium 3 The N interface layer effectively improves the instability of electrolyte to Li, inhibits the growth of lithium dendrite and improves the low ionic conductivity of the traditional buffer layer.
The integrated solid electrolyte has quick Li + The transmission channel, the electronic insulation and the chemical stability between the lithium ion battery and the metal Li effectively inhibit the interface reaction between the LAGP electrolyte and the metal lithium, promote the development of the high-stability all-solid-state lithium battery, and provide a tamping foundation for the mass production of the lithium ion battery through the controllability and the operability of the magnetron sputtering.
Drawings
Fig. 1: the invention discloses a structural schematic diagram of an all-solid-state thin-film lithium ion battery.
Fig. 2: surface morphology and cross-sectional morphology of the LAGP electrolyte dense layer in example 1.
Fig. 3: cross-sectional morphology of the LAGP-LiPON electrolyte gradient buffer layer in example 1.
Fig. 4: impedance plot for Cu/LAGP/Cu symmetric cells in example 3.
Fig. 5: cycling diagram of Li/LAGP/Li symmetric cells in example 4.
Fig. 6: the discharge capacity of the all solid state lithium ion battery in example 5 is plotted against cycle number.
Detailed Description
The following examples further illustrate the technical aspects of the present invention, but are not intended to limit the scope of the present invention.
The embodiment provides an all-solid-state thin film type lithium ion battery, and a structural schematic diagram is shown in the attached figure 1; consists of a positive electrode, a LAGP electrolyte compact layer, a LAGP-LiPON electrolyte gradient buffer layer, li 3 The N interface modification layer and the negative electrode are assembled in sequence; the positive electrode material is lithium cobalt oxide or lithium iron phosphate; the negative electrode is lithium metal.
The specific embodiment also provides a preparation method of the integrated solid electrolyte, which comprises the following steps:
(1) Placing a target substrate in absolute ethyl alcohol for ultrasonic cleaning, drying, cutting into a certain size according to requirements, and fixing the size on a deposition substrate in a magnetron sputtering chamber;
(2) Fixing a LAGP target, and uniformly depositing a LAGP electrolyte film layer on the surface of the substrate by utilizing a magnetron sputtering technology;
(3) Regulating the atmosphere content ratio (Ar/O) in the chamber 2 ) Optimizing the film morphology and the atomic distribution of the LAGP electrolyte layer;
(4) Regulation of Ar and O 2 Optimizing the sputter deposition speed and the atomic stack condition of the LAGP electrolyte layer;
(5) Regulating and controlling three parameters of sputtering power, sputtering chamber pressure and target distance, and optimizing the deposition rate and P/Ge ratio of the LAGP electrolyte layer;
(6) Regulating and controlling sputtering time, and optimizing the thickness of the LAGP electrolyte layer;
(7) After the parameters are determined to be the preferred values, moving the LAGP electrolyte layer after sputter deposition to a muffle furnace for sintering treatment, optimizing the sintering temperature, the heating rate and the heat preservation time of the LAGP electrolyte layer, and regulating and controlling the crystal orientation, the compactness and the ion conductivity of the crystalline LAGP;
(8) Depositing a LiPON-LAGP gradient buffer layer on the surface of the crystalline LAGP electrolyte layer by a double-target sputtering technology, regulating and controlling sputtering power and time, and optimizing concentration gradient change and thickness of the gradient buffer layer;
(9) A certain amount of molten lithium is dripped on the buffer layer surface of the integrated electrolyte, and the temperature and the in-situ reaction time of the molten lithium are regulated and controlled to construct an interface modification layer Li at the negative electrode side by utilizing the in-situ reaction between LiPON and the molten lithium 3 N。
Specifically, the target substrate in the step 1) is a substrate (current collector) such as a silicon wafer, carbon paper, carbon cloth, and the like, and the target size is cut into a circular substrate with the diameter of 14cm and a square substrate with the size of 2cm×2cm according to the requirements of the subsequent button cell and the soft package cell.
Specifically, the processing method of the substrate in the step 1) is as follows: cutting a substrate into square substrates with the length of 2cm multiplied by 2cm, sequentially placing the square substrates in absolute ethyl alcohol and ultrapure water for ultrasonic cleaning for 10-30 min, fixing a Si substrate with the length of 2cm multiplied by 2cm on a substrate frame in a magnetron sputtering chamber after vacuum drying, and further purging the surfaces of the substrates with nitrogen gas to wait for the subsequent sputtering operation of the LAGP electrolyte layer.
Specifically, the LAGP target in the step 2) is a molar ratio of 3:1:3:6 (Li: al: ge: P).
Specifically, ar/O in the step 3) 2 The ratio range is 3:1 to 1:3.
specifically, the total gas flow rate of the magnetron sputtering in the step 4) is 20 sccm-60 sccm.
Specifically, the sputtering power in the step 5) is 40-160W, the chamber pressure is 0.5-1 Pa, and the target distance is 6-10 cm.
Specifically, the deposition optimization of the LAGP electrolyte layer in the step 5) is cooperatively regulated and controlled based on the influence rule of sputtering power, chamber pressure and target electrode distance on the deposition rate and the P/Ge ratio of the target electrolyte layer, so as to efficiently prepare the LAGP electrolyte layer with the proper P/Ge ratio. Wherein the P/Ge ratio decreases with increasing power and increases with increasing pressure; the deposition rate increased with increasing power, and the pressure tended to increase and decrease with increasing pressure, tending toward the optimum value around 0.5 Pa.
Specifically, the sputtering time in the step 6) is 1 to 24 hours;
specifically, the sintering temperature in the step 7) is 750-950 ℃, the heating rate is 2-10 ℃/min, and the heat preservation time is 3-8 h;
specifically, the sintering curve in the step 7) is determined based on the law of influence of the sintering temperature and the temperature rising rate on the crystallinity and the density of the LAGP electrolyte, and the optimal sintering curve is determined based on the difference of the high-temperature shrinkage rates of different atoms and oxides thereof and the ionic conductivity of the grain boundary/crystal phase. The faster the temperature rising rate is, the shorter the material diffusion time of the LAGP sputtering layer is, so that the local temperature is higher, and the sintering-like pores are more. The sintering temperature is too low to ensure smooth particle mass transfer, so that the grain size is small, the porosity is high, and the density of the sintered sample is low. However, when the sintering temperature exceeds the critical temperature, the sintering sample may be excessively burned or a part of the oxide may be melted, resulting in a decrease in the density of the sintering sample.
Specifically, the buffer layer construction in the step 8) is performed by adjusting Li 3 PO 4 The sputtering time and sputtering power of the target and the LAGP target are realized and controlled, and the constructed buffer layer presents a gradient type variation trend of high LAGP concentration at the electrolyte side and high LiPON content at the lithium cathode side.
Specifically, in the sputtering process of the gradient buffer layer in the step 8), the optimal parameters of the LAGP sputtered layer are adopted for both the sputtering power and the target electrode distance of LiPON. The sputtering time of LiPON is 0.5 h-3 h, the sputtering time of LAGP is 1 h-5 h, and the sputtering time of LiPON is 0.5-1.5 h later than LAGP in the sputtering process.
Specifically, the in-situ chemical reaction temperature of the LAGP-LiPON electrolyte buffer layer and the molten lithium in the step 9) is 200-400 ℃; the reaction time is 1 min-3 min.
The obtained integrated electrolyte comprises a LAGP electrolyte compact layer, a LAGP-LiPON electrolyte gradient buffer layer and in-situ constructed Li 3 And an N interface modification layer. Further, in order to prepare an all-solid-state lithium ion battery based on an integrated electrolyte, a matrix is replaced by lithium iron phosphate and lithium cobaltate prepared through magnetron sputtering, subsequent operation is carried out, and after molten lithium and LiPON react in situ, polyurethane is used for illumination packaging.
Example 1
The embodiment provides an integrated electrolyte layer, and the preparation method thereof comprises the following steps:
s1, sequentially placing Si sheets in absolute ethyl alcohol and deionized water for ultrasonic cleaning, vacuum drying, cutting into square substrates of 2cm multiplied by 2cm, fixing the cut Si sheets on a substrate table, and waiting for Li to be added 1.5 Al 0.5 Ge 1.5 (PO 4 ) 3 After the target is fixed, the target pole distance is adjusted to 7cm, the sputtering chamber is closed, and vacuum is pumped. To reduce the pressure in the chamber to 1 x 10 -4 The vacuum operation is stopped at Pa, and the pressure is used as the sputtering base pressure. Continuously, ar and O are respectively regulated 2 The gas flow rate of (15 sccm Ar,5sccm O) 2 ) So that Ar within the magnetron sputtering chamber: o (O) 2 The atmosphere ratio was adjusted to 3:1, at which time the sputtering pressure in the chamber was 0.6Pa. And (3) performing magnetron sputtering in a radio frequency mode, wherein the sputtering power is set to be 60W, the baffle plate of the substrate table is removed after the sputtering is performed for 15min, and the rotary button of the substrate table is opened, so that uniform sputtering of the LAGP is facilitated, and the sputtering time is set to be 10h. The LAGP electrolyte compact layer is obtained, the surface morphology is shown in figure 2, and the thickness is 960nm.
S2, adopting double-target sputtering to respectively adjust LAGP target and Li 3 PO 4 And closing the sputtering chamber and vacuumizing, wherein the target distance (7 cm) between the target and the substrate table is equal to that between the target and the substrate table. To reduce the pressure in the chamber to 1 x 10 -4 And stopping vacuumizing operation when Pa, slowly conveying 20sccmAr into the chamber to increase the sputtering pressure to 0.6Pa, and starting sputtering. At this time, the dual targets all adopt a radio frequency mode, the initial sputtering power of LAGP is set to be 60W, li 3 PO 4 Setting the initial sputtering power of (2) to 40W, starting the LAGP sputtering program first, and starting Li after 1h 3 PO 4 The sputtering power of the double targets is adjusted every 0.5h, the power change gradient of LAGP is-5W, li 3 PO 4 The power change gradient of (2) is 5W, sputtering is stopped after co-sputtering for 4h, and the target electrolyte is moved out of the magnetron sputtering chamber. The cross-sectional morphology diagram of the obtained LAGP-LiPON electrolyte gradient buffer layer is shown in figure 3.
S3, integrating the solid statePlacing the electrolyte on a heating table of a glove box, sputtering the LiPON with the side facing upwards, melting 1g of metallic lithium at high temperature, then dripping the molten lithium onto the surface of the electrolyte, uniformly adsorbing the molten lithium by utilizing the capillary action and the lithium affinity of the LiPON, and performing in-situ reaction for 1min to form Li 3 And the N interface modification layer is tightly contacted by loading polyimide packaging materials under the pressure of 6 MPa.
Example 2
The embodiment provides an integrated electrolyte layer, and the preparation method thereof comprises the following steps:
s1, sequentially placing Si sheets in absolute ethyl alcohol and deionized water for ultrasonic cleaning, vacuum drying, cutting into square substrates of 2cm multiplied by 2cm, fixing the cut Si sheets on a substrate table, and waiting for Li to be added 1.5 Al 0.5 Ge 1.5 (PO 4 ) 3 After the target is fixed, the target pole distance is adjusted to 7cm, the sputtering chamber is closed, and vacuum is pumped. To reduce the pressure in the chamber to 1 x 10 -4 The vacuum operation is stopped at Pa, and the pressure is used as the sputtering base pressure. Continuously, ar and O are respectively regulated 2 The gas flow rate of (15 sccm Ar,5sccm O) 2 ) So that Ar within the magnetron sputtering chamber: o (O) 2 The atmosphere ratio was adjusted to 3:1, at which time the sputtering pressure in the chamber was 0.6Pa. And (3) performing magnetron sputtering in a radio frequency mode, wherein the sputtering power is set to be 60W, the baffle plate of the substrate table is removed after the sputtering is performed for 15min, and the rotary button of the substrate table is opened, so that uniform sputtering of the LAGP is facilitated, and the sputtering time is set to be 16h, so that the LAGP electrolyte sputtering layer with the thickness of 1 mu m is obtained.
S2, after the sputtering procedure is finished, transferring the sputtered LAGP electrolyte to an atmosphere furnace, and performing Ar/O (atomic oxygen) treatment on the LAGP electrolyte 2 And in the atmosphere, the densification of the LAGP electrolyte is completed according to a designed sintering curve. The heating rate was set at 5 ℃/min, the densification temperature was set at 850 ℃, the sintering time was set at 120 minutes, and the densified LAGP solid electrolyte film was collected after the sintering procedure was completed.
S3, after the program is finished, the compact LAGP electrolyte is fixed on a substrate fixing table of magnetron sputtering again, gradient sputtering is carried out through double targets, and the LAGP targets and Li are respectively adjusted 3 PO 4 Target and target electrode of substrate tableFrom (7 cm), the sputtering chamber was closed and evacuated. To reduce the pressure in the chamber to 1 x 10 -4 And stopping vacuumizing operation when Pa, slowly conveying 20sccmAr into the chamber to increase the sputtering pressure to 0.6Pa, and starting sputtering. At this time, the dual targets all adopt a radio frequency mode, the initial sputtering power of LAGP is set to be 60W, li 3 PO 4 Setting the initial sputtering power of (2) to 40W, starting the LAGP sputtering program first, and starting Li after 1h 3 PO 4 The sputtering power of the double targets is adjusted every 0.5h, the power change gradient of LAGP is-5W, li 3 PO 4 The power change gradient of (2) is 5W, sputtering is stopped after co-sputtering for 4h, and the target electrolyte is moved out of the magnetron sputtering chamber, so that the integrated electrolyte consisting of the LAGP electrolyte compact layer and the LAGP-LiPON electrolyte gradient buffer layer is obtained.
S4, after sputtering, placing the integrated electrolyte in a glove box to enable the LiPON electrolyte layer and the molten lithium to react in situ to construct Li 3 And an N interface modification layer. Specifically, the integrated solid electrolyte is placed on a heating table of a glove box, one side of the integrated solid electrolyte sputtered with LiPON faces upwards, 1g of metal lithium is melted at high temperature and then is dripped on the surface of the electrolyte, the molten lithium is uniformly adsorbed by utilizing the capillary action and the lithium affinity of the LiPON, and after in-situ reaction is carried out for 1min, polyimide packaging materials are selected to load the pressure of 6MPa, so that the close contact is realized.
Example 3
The embodiment provides a symmetrical battery, and the preparation method comprises the following steps:
s1, ultrasonically cleaning a conductive copper foil with absolute ethyl alcohol, vacuum drying, cutting into a round substrate with the diameter of 14cm, fixing the cut copper foil on a substrate table, and waiting for Li to be removed 1.5 Al 0.5 Ge 1.5 (PO 4 ) 3 After the target is fixed, the target electrode distance is adjusted to 6cm, the sputtering chamber is closed, and vacuum is pumped. To reduce the pressure in the chamber to 1 x 10 -4 The vacuum operation is stopped at Pa, and the pressure is used as the sputtering base pressure. Continuously, ar and O are respectively regulated 2 Gas flow rate of (15 sccmAr,5 sccmO) 2 ) So that Ar within the magnetron sputtering chamber: o (O) 2 The atmosphere ratio is adjusted to 3:1, and sputtering is performed in the chamber at the momentThe pressure was 0.6Pa. And (3) performing magnetron sputtering in a radio frequency mode, wherein the sputtering power is set to be 60W, the baffle plate of the substrate table is removed after the sputtering is performed for 15min, and the rotary button of the substrate table is opened, so that uniform sputtering of the LAGP is facilitated, and the sputtering time is set to be 16h, so that the LAGP electrolyte sputtering layer with the thickness of 1 mu m is obtained.
S2, after the sputtering procedure is finished, transferring the sputtered LAGP electrolyte to an atmosphere furnace, and completing densification of the LAGP electrolyte in Ar gas according to a designed sintering curve. The heating rate was set at 5 ℃/min, the densification temperature was set at 850 ℃, the sintering time was set at 120 minutes, and the densified LAGP solid electrolyte film was collected after the sintering procedure was completed.
S3, after the program is finished, the compact LAGP electrolyte is fixed on a substrate fixing table of magnetron sputtering again, gradient sputtering is carried out through double targets, and the LAGP targets and Li are respectively adjusted 3 PO 4 And closing the sputtering chamber and vacuumizing, wherein the target distance (7 cm) between the target and the substrate table is equal to that between the target and the substrate table. To reduce the pressure in the chamber to 1 x 10 -4 And stopping vacuumizing operation when Pa, slowly conveying 20sccmAr into the chamber to increase the sputtering pressure to 0.6Pa, and starting sputtering. At this time, the dual targets all adopt a radio frequency mode, the initial sputtering power of LAGP is set to be 60W, li 3 PO 4 Setting the initial sputtering power of (2) to 40W, starting the LAGP sputtering program first, and starting Li after 1h 3 PO 4 The sputtering power of the double targets is adjusted every 0.5h, the power change gradient of LAGP is-5W, li 3 PO 4 The power change gradient of (2) is 5W, sputtering is stopped after co-sputtering for 4h, and the integrated electrolyte consisting of the LAGP electrolyte compact layer and the LAGP-LiPON electrolyte gradient buffer layer is obtained.
S4, after preparation of the target integrated electrolyte is completed, fixing a Cu target, sputtering by adopting a direct current sputtering mode, uniformly depositing a conductive Cu film on the LiPON side of the integrated electrolyte, wherein the sputtering power is set to be 40W, and the sputtering time is set to be 10 minutes.
S5, after sputtering, placing the integrated electrolyte plated with the copper film in a glove box, assembling the integrated electrolyte into a symmetrical battery by using a button battery shell, and loading 12MPa pressure to realize close contact based on DeThe national Zahner electrochemical workstation carries out electrochemical impedance test on the symmetrical battery, and selects EIS mode and 0.1 Hz-10 6 The test frequency range of Hz gives an electrolyte with an ohmic impedance of approximately 700 Ω and an electrochemical impedance of 1200 Ω, as shown in fig. 4.
Example 4
The embodiment provides a symmetrical battery, and the preparation method comprises the following steps:
s1, conducting carbon cloth is ultrasonically cleaned by absolute ethyl alcohol, vacuum-dried and cut into round substrates with the diameter of 14cm, the cut carbon cloth is fixed on a substrate table, and Li is reserved 1.5 Al 0.5 Ge 1.5 (PO 4 ) 3 After the target is fixed, the target electrode distance is adjusted to 6cm, the sputtering chamber is closed, and vacuum is pumped. To reduce the pressure in the chamber to 1 x 10 -4 The vacuum operation is stopped at Pa, and the pressure is used as the sputtering base pressure. Continuously, ar and O are respectively regulated 2 Gas flow rate of (15 sccmAr,5 sccmO) 2 ) So that Ar within the magnetron sputtering chamber: o (O) 2 The atmosphere ratio was adjusted to 3:1, at which time the sputtering pressure in the chamber was 0.6Pa. And (3) performing magnetron sputtering in a radio frequency mode, wherein the sputtering power is set to be 60W, the baffle plate of the substrate table is removed after the sputtering is performed for 15min, and the rotary button of the substrate table is opened, so that uniform sputtering of the LAGP is facilitated, and the sputtering time is set to be 16h, so that the LAGP electrolyte sputtering layer with the thickness of 1 mu m is obtained.
S2, after the sputtering procedure is finished, transferring the sputtered LAGP electrolyte to an atmosphere furnace, and completing densification of the LAGP electrolyte in Ar gas according to a designed sintering curve. The heating rate was set at 5 ℃/min, the densification temperature was set at 850 ℃, the sintering time was set at 120 minutes, and the densified LAGP solid electrolyte film was collected after the sintering procedure was completed.
S3, after the program is finished, the compact LAGP electrolyte is fixed on a substrate fixing table of magnetron sputtering again, gradient sputtering is carried out through double targets, and the LAGP targets and Li are respectively adjusted 3 PO 4 And closing the sputtering chamber and vacuumizing, wherein the target distance (7 cm) between the target and the substrate table is equal to that between the target and the substrate table. To reduce the pressure in the chamber to 1 x 10 -4 Stopping vacuumizing operation in Pa, and slowly conveying into the chamberThe sputtering pressure was increased to 0.6Pa by 20sccmAr, and sputtering was started. At this time, the dual targets all adopt a radio frequency mode, the initial sputtering power of LAGP is set to be 60W, li 3 PO 4 Setting the initial sputtering power of (2) to 40W, starting the LAGP sputtering program first, and starting Li after 1h 3 PO 4 The sputtering power of the double targets is adjusted every 0.5h, the power change gradient of LAGP is-5W, li 3 PO 4 The power change gradient of (2) is 5W, sputtering is stopped after co-sputtering for 4h, and the integrated electrolyte consisting of the LAGP electrolyte compact layer and the LAGP-LiPON electrolyte gradient buffer layer is obtained.
S4, after preparation of the target electrolyte is completed, sputtering is finished, the integrated electrolyte taking the conductive carbon cloth as a matrix is placed in a glove box, the cathode is selected from molten lithium infiltrated by the same batch of conductive carbon cloth, a button cell shell is selected for assembling a symmetrical cell, and 12MPa pressure is loaded to realize close contact, so that the cell is assembled for cyclic test. As shown in FIG. 5, the Li/LAGP/Li symmetric battery was at 0.5mA/cm 2 Can stably circulate for more than 700 hours under the current, and the polarization voltage in the circulation process is lower than 0.015V.
Example 5
The embodiment provides an all-solid-state thin-film lithium ion battery, and the preparation method comprises the following steps:
s1, ultrasonically cleaning an aluminum foil with absolute ethyl alcohol, vacuum drying, cutting into round substrates with the diameter of 14cm, fixing the cut aluminum foil on a substrate table, and waiting for LiCoO 2 After the target is fixed, adjusting the target distance to 7cm, closing the sputtering chamber, and vacuumizing. To reduce the pressure in the chamber to 1 x 10 -4 The vacuum operation is stopped at Pa, and the pressure is used as the sputtering base pressure. Further, a total gas flow of 70sccm was introduced into the chamber to adjust Ar/O 2 And (3) performing radio frequency mode sputtering according to the ratio of 6:1, and stopping the program sputtering after 6 hours.
S2, after the steps are finished, li is added 1.5 Al 0.5 Ge 1.5 (PO 4 ) 3 After the target is fixed, the target pole distance is adjusted to 7cm, the sputtering chamber is closed, and vacuum is pumped. To reduce the pressure in the chamber to 1 x 10 -4 Stopping the vacuumizing operation at Pa, andthis pressure was used as the sputtering base pressure. Continuously, ar and O are respectively regulated 2 Gas flow rate of (15 sccmAr,5 sccmO) 2 ) So that Ar within the magnetron sputtering chamber: o (O) 2 The atmosphere ratio was adjusted to 3:1, at which time the sputtering pressure in the chamber was 0.6Pa. And (3) performing magnetron sputtering in a radio frequency mode, wherein the sputtering power is set to be 60W, the baffle plate of the substrate table is removed after the sputtering is performed for 15min, and the rotary button of the substrate table is opened, so that uniform sputtering of the LAGP is facilitated, and the sputtering time is set to be 16h, so that the LAGP electrolyte sputtering layer with the thickness of 1 mu m is obtained.
S3, after all sputtering procedures are finished, sputtering LiCoO 2 Transferring the LAGP film to an atmosphere furnace at Ar/O 2 And in the gas, the densification of the LAGP electrolyte is completed according to a designed sintering curve. The heating rate was set at 5 ℃/min, the densification temperature was set at 850 ℃, the sintering time was set at 120 minutes, and the densified LAGP solid electrolyte film was collected after the sintering procedure was completed.
S4, after the program is finished, the compact LAGP electrolyte is fixed on a substrate fixing table of magnetron sputtering again, gradient sputtering is carried out through double targets, and the LAGP targets and Li are respectively adjusted 3 PO 4 And closing the sputtering chamber and vacuumizing, wherein the target distance (7 cm) between the target and the substrate table is equal to that between the target and the substrate table. To reduce the pressure in the chamber to 1 x 10 -4 And stopping vacuumizing operation when Pa, slowly conveying 20sccmAr into the chamber to increase the sputtering pressure to 0.6Pa, and starting sputtering. At this time, the dual targets all adopt a radio frequency mode, the initial sputtering power of LAGP is set to be 60W, li 3 PO 4 Setting the initial sputtering power of (2) to 40W, starting the LAGP sputtering program first, and starting Li after 1h 3 PO 4 The sputtering power of the double targets is adjusted every 0.5h, the power change gradient of LAGP is-5W, li 3 PO 4 The power change gradient of (2) is 5W, sputtering is stopped after co-sputtering for 4h, and the integrated electrolyte consisting of the LAGP electrolyte compact layer and the LAGP-LiPON electrolyte gradient buffer layer is obtained.
S5, after the preparation of the target half battery is completed, sputtering is finished, and the prepared half battery is placed in a glove box, so that LiPON electrolyte layer and molten lithium react in situ to construct Li 3 N interfaceAnd (3) a modification layer. Specifically, the integrated solid electrolyte is placed on a heating table of a glove box, one side of the integrated solid electrolyte sputtered with LiPON faces upwards, 1g of metal lithium is melted at high temperature and then is dripped on the surface of the electrolyte, the molten lithium is uniformly adsorbed by utilizing the capillary action and the lithium affinity of the LiPON, after in-situ reaction is carried out for 1min, polyimide packaging materials are selected to load 6MPa pressure to realize close contact, and finally the integrated solid film type lithium ion battery is assembled.
The graph of the variation of the discharge capacity of the all-solid-state lithium ion battery obtained in this example with the cycle number is shown in fig. 6. The first-cycle discharge capacity of the all-solid-state lithium ion battery is up to 160mAh/g, and stable discharge capacity can be still provided along with the circulation, and the discharge capacity of the battery can still be stabilized at 140mAh/g even if the circulation is carried out for 60 times.
Claims (8)
1. An all-solid-state film type lithium ion battery is characterized by comprising a positive electrode, a LAGP electrolyte compact layer, a LAGP-LiPON electrolyte gradient buffer layer and Li 3 The N interface modification layer and the negative electrode are assembled in sequence; the positive electrode material is lithium cobalt oxide or lithium iron phosphate; the negative electrode is lithium metal.
2. The all-solid-state thin-film lithium ion battery of claim 1, wherein the thickness of the langp electrolyte compact layer is 0.4-2 μm; the thickness of the gradient LAGP-LiPON electrolyte gradient buffer layer is 200-400 nm; the Li is 3 The thickness of the N interface modification layer is 5-20 nm.
3. The method for preparing the all-solid-state thin-film lithium ion battery as claimed in claim 1, which is characterized by comprising the following steps:
1) By Li 1+x Al x Ge 2-x (PO 4 ) 3 Performing magnetron sputtering on the target material, and then placing the target material in a muffle furnace for sintering treatment to prepare a LAGP electrolyte compact layer;
2) Depositing a LAGP-LiPON electrolyte gradient buffer layer on the surface of the LAGP electrolyte compact layer;
3) Construction of Li on the negative lithium electrode side by in-situ chemical reaction of LiPON and molten lithium 3 An N interface modification layer;
4) And the lithium ion battery is assembled with a metal lithium anode and a metal lithium cathode in a lamination way to form an all-solid-state thin-film lithium ion battery.
4. The method for preparing an all-solid-state thin-film lithium ion battery according to claim 3, wherein the LAGP electrolyte in step 1 is a NICSION-type electrolyte, specifically Li 1.5 Al 0.5 Ge 1.5 (PO 4 ) 3 。
According to the scheme, the target material of the LAGP electrolyte in the step 1 is Li 2 O、Al 2 O 3 、GeO 2 、P 2 O 5 The purity of the target material is 99.99%, the diameter of the target material is 50.8mm, and the thickness is 3.0mm; one side is tightly connected with copper targets with the same size and thickness of 1mm by metal indium;
the magnetron sputtering conditions include: the magnetron sputtering power is 40-160W, the magnetron sputtering temperature is 25-100 ℃, the target electrode distance is 6-10 cm, the magnetron sputtering pressure is 0.5-1 Pa, and the magnetron sputtering time is 1-24 h.
5. The method for preparing an all-solid-state thin-film lithium ion battery according to claim 3, wherein the muffle furnace sintering treatment conditions in step 1 comprise: the temperature rising rate is 2-10 ℃/min, the densification temperature is 750-950 ℃, and the heat preservation time is 3-8 h.
6. The method for preparing an all-solid-state thin-film lithium ion battery according to claim 3, wherein the sputtering step of the LAGP-LiPON electrolyte gradient buffer layer in step 2 comprises: adopting a double-target sputtering mode, and respectively carrying out target LAGP and target Li under nitrogen atmosphere 3 PO 4 The gradient electrolyte buffer layer is fixed at two ends of a magnetron sputtering instrument chamber, the sputtering conditions are regulated and controlled by taking time as a control variable, and the gradient electrolyte buffer layer with high concentration of LAGP at the electrolyte side and high content of LiPON at the cathode side is constructed.
7. The method for preparing an all-solid-state thin-film lithium ion battery according to claim 6, wherein the sputtering time of LiPON is 0.5-3 h, the sputtering time of LAGP is 1-5 h, and the sputtering time of LiPON is 0.5-1.5 h later than LAGP in the sputtering process.
8. The method for preparing an all-solid-state thin-film lithium ion battery according to claim 3, wherein the in-situ chemical reaction temperature of the LAGP-LiPON electrolyte buffer layer and the molten lithium in the step 3 is 200-400 ℃; the reaction time is 1 min-3 min.
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