CN108511543A - A kind of integrated energy resource supply product and preparation method thereof and equipment - Google Patents

Abstract

The invention provides an integrated energy supply product, which is the integration of III-V thin-film solar cells and all-solid-state thin-film lithium batteries. Current collector, the positive and negative current collectors of the lithium battery are connected to the load through wires. The present invention also provides a preparation method for energy supply products and equipment for preparing energy supply products, including a glove box in which magnetron sputtering coating equipment, vacuum evaporation equipment and hot pressing equipment are integrated. The energy supply product of the present invention adopts III-V thin-film solar cells and a flexible substrate with light weight. The overall thickness of the solar cells is less than 200 microns, and the weight-area ratio is 300 g/m ² , which is far smaller than the weight-area of crystalline silicon cells. Compared with; thin-film all-solid-state lithium battery, the substrate is flexible; the thickness of the entire energy supply product is within 1 mm, flexible, light and easy to carry.

Description

An integrated energy supply product and its preparation method and equipment

technical field

The invention belongs to the field of energy technology, and in particular relates to an energy supply product integrated with a solar battery and a lithium battery, and a preparation method and equipment thereof.

Background technique

With the increasing thinness of electronic products, the power supply devices are increasingly required to be thin, safe, and efficient. At present, most of the batteries in electronic products such as mobile phones and computers have problems such as short battery life, large volume, and heavy weight, which restrict the development of electronic products. the bottleneck. In order to achieve a longer battery life, some inventions combine solar cells with lithium batteries, which can use the continuous energy of the sun's light source to achieve unlimited battery life, such as patents CN 105789723A and CN105789372A, which combine copper indium gallium selenide flexible solar cells The combination of batteries can convert solar light energy into electrical energy at any time, and then store it in lithium batteries to power electronic products. However, the currently available photoelectric conversion efficiency of copper indium gallium selenide solar modules is generally about 15%, which cannot well meet the needs of current electronic products; in addition, the electrolyte of thin film lithium batteries prepared in previous patents is generally lithium hexafluorophosphate ( LiPF ₆ ) or lithium perchlorate (LiClO ₄ ) and other organic solutions or gels of lithium salts are flammable and explosive at high temperatures: lithium batteries combined with solar energy must be exposed to the sun for a long time, and the temperature It often reaches 40-50 degrees Celsius. At this temperature, the liquid organic electrolyte may be heated to volatilize gas or expand, causing the battery to bulge or even explode.

The functions of current electronic products are becoming more and more powerful, and the demand for energy is also increasing. The poor battery life of traditional secondary batteries has become a bottleneck in the development of electronic products. Using the combination of flexible solar cells and flexible lithium batteries, energy harvesting and energy storage are combined, as long as there is sunlight, it can be charged, and energy can be stored anytime and anywhere to ensure the normal operation of electronic products. Since the low-light performance of the III-V solar cell is better, it can also be charged indoors. In addition, the all-solid-state lithium battery has the characteristics of high energy density, and the battery of the same volume can store more electric energy to prolong the battery life.

Traditional batteries have safety hazards. In the high temperature environment of traditional lithium batteries, the liquid electrolyte is easy to release chemical gas, which leads to the expansion of the battery, and the growth of common lithium dendrites, etc., are all causes of battery explosion. When a traditional lithium battery is integrated with a solar cell, the temperature of the battery is likely to reach 40-50°C due to long-term exposure to the sun. The common liquid electrolyte is usually an organic solution of lithium salt, which is easy to release gas at high temperature. In the environment, bulges or even explosions will occur, causing harm to the human body.

Traditional energy supply equipment also has the disadvantage of large volume and heavy weight, which is not conducive to the miniaturization and portability of electronic equipment. In addition, traditional energy supply equipment is generally not flexible. In the past, there were also thin-film lithium batteries prepared by spraying, which were less bendable and not flexible in the true sense. It is easy to cause battery failure.

Contents of the invention

The purpose of the present invention is to provide an integrated energy supply product aiming at the deficiencies in the art.

A second object of the present invention is to provide a method for preparing the integrated energy supply product.

A third object of the invention is to propose a plant for the preparation of an all-in-one energy supply product.

To achieve the above object, the technical solution of the present invention is

An integrated energy supply product, which is the integration of III-V thin-film solar cells and all-solid-state thin-film lithium batteries. The positive electrode (p junction) of the solar cell is connected to the positive electrode collector of the lithium battery, and the negative electrode (n junction) of the solar cell A current collector connected to the negative electrode Li of the lithium battery;

The lithium battery is provided with a flexible metal foil substrate, the solar battery is provided with an organic flexible substrate, and the flexible substrate of the lithium battery and the organic flexible substrate of the solar battery are bonded together.

The positive and negative current collectors of the lithium battery are connected to the load through wires.

The invention adopts an all-solid-state lithium battery, replaces the liquid electrolyte with a solid electrolyte, and has a stable working temperature between -20°C and 60°C. It is non-flammable, non-volatile, and non-leakage at high temperatures, and it also inhibits the growth of lithium dendrites. There will be a short circuit hazard, so the stability and safety are greatly improved.

Wherein, the gallium arsenide thin-film solar cell is upward from the organic flexible substrate, followed by a back metal with a thickness of 30-50nm, a bottom cell InGaAs with a thickness of 150-200nm, a buffer layer InAlGaAs with a thickness of 100-300nm, and a tunnel with a thickness of 20-80nm. Junction AlGaAs, thickness 100-200nm top cell GaInP, thickness 30-50nm AlInP window layer, thickness 20-50nm front electrode, thickness 20-50nm antireflection film, 50-80μm front barrier film.

A preferred technical solution of the present invention is that in the III-V thin-film solar cell, the window layer is n-type Al _0.3 In _0.7 P, and the doping concentration is (0.5-2)×10 ¹⁹ cm ^-3 ; the emission region is n-type Ga _0.5 In _0.5 P, doping concentration (0.5-2)×10 ¹⁸ cm ^-3 ; base region is p-type Ga _0.5 In _0.5 P, doping concentration (0.5-2)×10 ¹⁸ cm ^-3 ; The tunnel junction is a p-type Ga _0.5 In _0.5 tunnel junction and an n-type Al _0.1 Ga _0.9 As tunnel junction, and the doping concentrations of the two tunnel junctions are independently (1-5)×10 ¹⁹ cm ^-3 ; the buffer layer is n Type In _x Al _y Ga _z As, 0≤x≤0.3, 0≤y≤0.1, 0.7≤z≤0.9, doping concentration (0.5-2)×10 ¹⁷ cm ^-3 ; bottom cell emitter is n-type In _0.3 Ga _0.7 As, the thickness is 100-200nm, the doping concentration is 1×10 ¹⁸ cm ^-3 ; the base region of the bottom cell is p-type In _0.3 Ga _0.7 As, the doping concentration is (0.5-2)×10 ¹⁸ cm ^-3 ; The back field is p-type In _0.3 Ga _0.7 As, and the doping concentration is (1-5)×10 ¹⁹ cm ^-3 .

Wherein, an anti-reflection film is deposited on the front of the III-V thin-film solar cell, and the material of the anti-reflection film is one or more of ITO, AZO, TiO ₂ , SiO ₂ ; the outer package of the anti-reflection film has Transparent waterproof membrane, the material of the transparent waterproof membrane is ETFE.

Wherein, the positive electrode of the lithium battery is LiCoO ₂ or LiMn ₂ O ₄ , the electrolyte is a LiPON solid electrolyte, and the positive electrode, negative electrode, electrolyte, and current collector of the lithium battery are made by magnetron sputtering and/or vapor deposition, respectively. .

Preferably, the lithium battery positive and negative current collectors are made together by magnetron sputtering, the thickness of the current collector is 50-200 nm, the thickness of the positive electrode is between 20-100 nm, the thickness of the electrolyte is between 100-200 nm, and the thickness of the negative electrode is 100-200nm.

The preparation method of the integrated energy supply product of thin-film solar cells and lithium batteries of the present invention includes the preparation of III-V thin-film solar cells and the preparation of all-solid-state thin-film lithium batteries. All-solid-state lithium-ion batteries and thin-film solar cells are integrated by pressure-mechanical bonding.

In the preparation method, EVA glue or other hot-press adhesive glues are mechanically stacked to integrate the all-solid-state lithium-ion battery and the thin-film solar battery that have been prepared separately. However, in the prior art, lithium-ion batteries are mostly prepared by coating the back of the thin-film solar cell or sputtering deposition on the substrate of the solar cell.

The advantage of this preparation method is as follows:

1) Since thin-film lithium batteries need to be prepared by subsequent annealing, they need to reach a high temperature of 300-400°C, which will have a certain impact on the thin-film crystal structure of solar cells, forming lattice defects, and then affecting the conversion efficiency of solar cells. In addition, the evaporation and sputtering methods used in the preparation of lithium batteries may cause elemental pollution to solar cells, resulting in loss of electrical properties of solar cells. The method of mechanical stacking avoids this disadvantage, and the lithium battery is prepared on an independent substrate and independent equipment, which ensures that the performance of the solar cell is not affected.

2) The equipment and process adopted are simple, there is little change in the existing process, the difficulty of product structure design is low, and it is easy to industrialize.

3) Using ultra-thin hot-press adhesive, it can still maintain flexibility after integration.

Wherein, the preparation method of the III-V thin-film solar cell is:

S1: cleaning and drying the semiconductor substrate; the semiconductor substrate is a GaAs substrate or a Ge substrate;

S2: The sacrificial layer, buffer layer, emitter layer, tunnel junction, and window layer are epitaxially grown on the substrate in sequence by MOCVD method. The reaction precursor gas introduced in the MOCVD process is arsine, phosphine, trimethylaluminum, and trimethylaluminum. Two or more of gallium-based and trimethylindium,

S3: The back metal is deposited on the epitaxial layer by magnetron sputtering, and a layer of flexible waterproof material is hot-pressed on the back metal as the transfer substrate of the epitaxial layer;

S4: peeling off the epitaxial layer from the substrate;

S5: Prepare the front electrode by screen printing on the front side of the solar cell,

S6: Deposit an anti-reflection film on the front of the solar cell by magnetron sputtering.

Wherein, the preparation method of the all-solid-state thin-film lithium battery is:

1) Put the metal foil into the magnetron sputtering chamber (the thickness of the metal foil used as the substrate is less than 100 microns, and it is flexible). The material of the metal foil is stainless steel, copper or silver, and it is sputtered on An insulating layer of Al ₂ O ₃ or SiO ₂ ;

2) Take out the sample, place it in the glove box, and use the positive and negative current collector shape masks, positive electrode shape masks, and electrolyte shape masks successively to make positive and negative electrode current collectors, positive electrodes, and electrolytes by magnetron sputtering. electrolyte;

3) Take the sample out of the magnetron sputtering equipment, remove the electrolyte mask in the glove box, and install the negative electrode shape mask, place it in the evaporation equipment, evaporate the negative electrode, then remove the negative electrode mask, and evaporate the organic protective layer ; The evaporation source used is PEN particles.

A device for preparing the integrated energy supply product, the device includes a glove box, and magnetron sputtering coating equipment, vacuum evaporation equipment and hot pressing equipment are integrated in the glove box, the Hot pressing equipment is used for waterproof packaging of solar cells, waterproof packaging of lithium batteries, and the overall integration of lithium batteries and solar energy.

In the method of the present invention, we have adopted an all-solid-state thin-film lithium battery preparation method. The electrolyte uses a solid inorganic thin film. The gas can ensure the safe and stable operation of the power supply equipment when it is exposed to the sun, and at the same time increase the density of energy storage. In addition, compared with the previous lithium battery patents combined with solar energy, in terms of preparation methods, we mainly adopt PVD coating methods such as sputtering, evaporation, etc., which avoids the difficulty of electrode and electrolyte film layers in the coating process of lithium batteries in the past. Failure caused by separation, the film layers of the lithium battery in the present invention are tightly combined, have a small thickness, and have good flexibility.

The beneficial effects of the integrated energy supply product of the present invention and its preparation method and equipment are as follows:

1. The energy supply product of the present invention adopts the III-V thin-film battery, and can adopt a flexible substrate with a lighter weight. The overall thickness of the solar cell is less than 200 microns, and the weight-to-area ratio is 300g/m ² , which is far smaller than that of ordinary crystalline silicon The weight-to-area ratio of the battery. The thickness of the entire power supply device after packaging can be controlled within 1 mm, and at the same time it is light and easy to carry. At present, a considerable part of the weight and volume of electronic products is composed of batteries. If the weight and volume of batteries can be reduced, a lot of space can be saved, and the entire equipment such as smart phones, smart watches, sensors, etc. can be reduced in size and weight. It is convenient for people to use and carry.

The combination of flexible solar cells and lithium batteries, combined with flexible OLED displays, will make flexible electronic devices possible and provide infinite possibilities for design. In the future, mobile phones, tablets, and computers will be able to be rolled or folded. Unfolded, it can also be integrated on carry-on clothes or bags, making it more flexible to use.

2. The present invention adopts the combination of solar energy and lithium battery, which can be charged as long as there is sunlight, so that energy can be stored uninterruptedly to ensure the normal operation of electronic products. Since the low-light performance of the III-V solar cell is better, it can also be charged indoors.

3. The present invention also fully considers the battery safety issue. When using a solar battery to charge, the temperature of the battery may reach 40-50°C due to the long-term exposure to the sun. The electrolyte of an ordinary lithium battery is usually an organic solvent of lithium salt, which will release gas at high temperature. In the environment, bulges or even explosions will occur, causing harm to the human body. The invention adopts an all-solid-state lithium battery, and replaces the liquid electrolyte with a solid electrolyte. The stable working temperature is -20°C-60°C. It is non-flammable, non-volatile, and non-leakage at high temperatures, and the growth of lithium dendrites is also greatly reduced. There will be no hidden danger of short circuit, so the stability and safety are greatly improved.

4. The open-circuit voltage and short-circuit current of solar cells of the III-V family can be controlled by connecting cells in series and in parallel, matching the charging voltage and current of lithium batteries;

5. The preparation of lithium batteries can also realize the series connection of multiple lithium batteries by repeating the deposition of positive and negative electrodes and electrolyte films to increase the voltage.

Description of drawings

FIG. 1 is a structural diagram of the epitaxial layer of a III-V solar cell.

Figure 2 is a schematic diagram of the structure of the glove box. 200 is a glove box, 201 is a magnetron sputtering coating equipment, 202 is a vacuum evaporation equipment, 203 is a hot pressing equipment, 204 is a transition chamber of the glove box, and 205 is a glove box station.

Fig. 3 is a top view of the mask, in which Fig. 3a is a positive and negative current collector shape mask 1, Fig. 3b is a positive electrode shape mask 2, Fig. 3c is an electrolyte shape mask 3, and Fig. 3d is a negative electrode shape mask 4.

Figure 4 shows the layer structure of a lithium battery chip. 400 is a metal substrate; 401 is an Al ₂ O ₃ film; 402 is a positive and negative current collector film; 403 is a positive electrode film; 404 is a LiPON solid electrolyte film; 405 is a Li negative electrode film; 406 is an organic protective film.

Fig. 5 is the circuit connection mode of the integrated energy supply product of the present thin-film solar cell and lithium battery.

Figure 6 is the lithium battery charging curve,

Figure 7 is the lithium battery discharge curve,

Figure 8 is the I-V curve of the solar cell array.

Detailed ways

The following examples are used to illustrate the present invention, but are not intended to limit the scope of the present invention.

Unless otherwise specified, the means used in the description are technical means known in the art.

The preparation method of the integrated energy supply product of the thin-film solar battery and the lithium battery of the present invention includes the preparation of the III-V thin-film solar battery and the preparation of the all-solid-state thin-film lithium battery. In a connected way, the all-solid-state lithium-ion battery and the thin-film solar battery are integrated. The equipment used is MOCVD (organic metal vapor deposition equipment), etching machine, laser scribing equipment, magnetron sputtering equipment, vacuum evaporation equipment, electroplating equipment, screen printing equipment, chemical stripping acid pool, PET/PSA thermal Sealing instrument, glove box, hot pressing equipment, etc.

The glove box 200 used for the integrated energy supply product of the present invention to prepare thin-film solar cells and lithium batteries is shown in FIG. device 203 . The glove box adopted in the present invention integrates magnetron sputtering coating equipment, vacuum evaporation equipment and hot pressing equipment in a glove box, considering that the LiPON electrolyte in the all-solid-state thin-film lithium battery is easy to react with water in the air In addition, Li metal as the negative electrode material is extremely unstable in water and oxygen, and the coating and packaging process needs to be transferred back and forth in different chambers and equipment, so the coating equipment and packaging equipment are placed in a glove Inside the box, it is convenient for coating and packaging to be carried out flexibly and safely, and ensures the stable performance of the battery. Among them, the hot pressing equipment 203 can be used not only for hot pressing bonding of lithium batteries and solar batteries, but also for waterproof packaging of solar batteries and aluminum-plastic film packaging of lithium batteries. In addition, a glove box is also provided in the glove box 200. transition bin 204 and glove box station 205.

Example 1

production material:

GaAs substrate, Ge substrate, aluminum plastic film, flexible PET or PEN film, EVA glue, reactive gases include arsine (AsH ₃ ), phosphine (PH ₃ ), trimethylaluminum (TMAl), trimethylgallium (TMGa), trimethylindium (TMIn), silane (SiH4), H ₂ S, diethyl zinc (DEZn), tetrachloromethane (CCl ₄ ), etc.; metal foils such as stainless steel, copper, silver, etc.; target Materials such as LiCoO ₂ , Li ₃ PO ₄ , Li ₂ MnO ₄ , Cu, Ag, Au, etc.; evaporation sources such as Li particles, Au particles, PEN organic evaporation sources, etc.

Preparation of triple-five double-junction cells:

S1. GaAs substrate cleaning and drying. Use acetone or alcohol with ultrasonic cleaning, and then put it in the dryer to dry.

The sacrificial layer, buffer layer, emitter layer, tunnel junction, window layer, etc. are epitaxially grown on the GaAs substrate by MOCVD (metal organic chemical vapor deposition) method. The precursor gas introduced in the MOCVD process is arsine ( _AsH3 ), phosphine (PH ₃ ), trimethylaluminum (TMAl), trimethylgallium (TMGa), trimethylindium (TMIn) and other gases are selected to react to form different compounds. One or more of silane (SiH ₄ ), H ₂ S, diethylzinc (DEZn) or tetrachloromethane (CCl ₄ ) is used for doping, and the growth sequence of the epitaxial layer is shown in Figure 1 (because the flexible three-five The family of thin films grows backwards, Figure 1 is the growth sequence, and the sequence of the structure from the PI substrate to the top is opposite).

Layer 100 is a GaAs substrate with a thickness of 200 μm, layer 101 is an AlAs sacrificial layer with a thickness of 50 nm; layer 102 is an n-type Al _0.3 In _0.7 P window layer with a thickness of 30-50 nm, and a doping concentration of 1×10 ¹⁹ cm ^{- 3} ; layer 103 is an n-type Ga _0.5 In _0.5 P emitter region with a thickness of 80nm and a doping concentration of 1×10 ¹⁸ cm ^-3 ; layer 104 is a p-type Ga _0.5 In _0.5 P base region with a thickness of 100nm and a doping concentration of 1× 10 ¹⁸ cm ^-3 ; layer 105 is a p-type Ga _0.5 In _0.5 P tunnel junction with a thickness of 20-50nm and a doping concentration of 2×10 ¹⁹ cm ^-3 ; layer 106 is an n-type Al _0.1 Ga _0.9 As tunnel junction with a thickness of 30nm, doping concentration 2×10 ¹⁹ cm ^-3 ; 107 is n-type In _x Al _y Ga _z As buffer layer, 0≤x≤0.3, 0≤y≤0.1, 0.7≤z≤0.9, thickness is 200nm, The doping concentration is 1×10 ¹⁷ cm ^-3 ; 108 is the n-type In _0.3 Ga _0.7 As bottom cell emission region, the thickness is 100-200nm, and the doping concentration is 1×10 ¹⁸ cm ^-3 ; the 109 layer is p-type In _0.3 Ga _0.7 As bottom cell base area with a thickness of 200nm and a doping concentration of 1×10 ¹⁸ cm ^-3 ; the 110 layer is p-type In _0.3 Ga _0.7 As back field with a thickness of 150nm and a doping concentration of 2×10 ¹⁹ cm ^-3 .

S2. The back metal Cu is deposited on the epitaxial layer by magnetron sputtering.

S3. Hot-press a layer of PI flexible waterproof material on the back metal, and at the same time serve as the transfer substrate of the epitaxial layer.

S4. The epitaxial layer is peeled off from the substrate by a selective etching method. Putting the battery into 10%-30% HF solution for 30 minutes, since the sacrificial layer AlAs is more easily corroded by acid solution, the epitaxial layer of the solar cell can be peeled off from the substrate.

S5. Prepare the front electrode by screen printing on the front side of the solar cell, using Cu metal material.

S6. Depositing a layer of ITO anti-reflection film on the front of the solar cell by magnetron sputtering.

S7. Take out the solar cells, cut them, and connect them in series or in parallel according to the product requirements to obtain the required voltage, about 4-5V.

S8. In the hot-press packaging equipment, the transparent waterproof flexible front film is used to package the front of the battery, that is, the anti-reflection film. The waterproof packaging film is made of ETFE material, the water permeability is less than 10 ^-3 g/m ² /day, the visible light transmittance is greater than 90%, and the thickness is 25μm-50μm.

In this embodiment, the flexible III-V battery is obtained by using the stripping method to obtain the III-V double-junction thin-film battery on the flexible polymer substrate, and the photoelectric conversion efficiency can reach 31% (AM1.5).

Preparation of all-solid-state thin-film lithium battery:

1) Put the metal foil into the magnetron sputtering chamber 201. The metal foil can be stainless steel with a thickness of 120±10 μm, coated with an insulating layer of Al ₂ O ₃ with a thickness of 100 nm. The vacuum degree of the sputtering chamber is 10 ^-6 Pa, the power is 15-20W, and the sample is left to cool in situ after coating.

2) Take the sample out and place it in the glove box 200, the glove box keeps the oxygen concentration less than 100ppm, and the water content is less than 100ppm; the positive and negative electrode current collector shape mask 1 (Fig. 3a, stainless steel mask, thickness about 100 microns, size The error is less than 100 microns) fixed on the sample, put it back into the magnetron sputtering chamber, and plate a Cu film with a thickness of about 100 nm.

3) Take the sample out, place it in the glove box, remove the positive and negative current collector shape mask 1, fix the positive electrode shape mask 2 (Figure 3b) on the sample, and put it back into the magnetron sputtering chamber. The target material is selected LiCO ₂ , deposited with a thickness of 50-60nm, forms the positive electrode of the lithium battery. After the deposition, the sample stage was heated to 450°C and annealed for about 15 minutes to obtain a film with uniform grain size, and then cooled naturally.

4) The sample is taken out from the magnetron sputtering equipment and directly enters the glove box, where the anode shape mask 2 is removed and the electrolyte shape mask 3 is fixed (Fig. 3c).

5) Put the sample into the magnetron sputtering coating device 201 again to prepare the electrolyte. N ₂ (0.5Pa) was passed through, the target material was Li ₃ PO ₄ , and a radio frequency power source was used to react to obtain a LiPON electrolyte film with a film thickness of 200nm.

6) The sample is taken out and placed in the glove box, the electrolyte shape mask 3 is removed, and the negative electrode shape mask 4 is fixed (Fig. 3d).

7) Put the sample into the vacuum evaporation equipment 202, and evaporate the lithium negative electrode. Lithium particles with a purity of 99.99% are used as the evaporation source, the pressure is 10 ⁻³ Pa, the heating temperature of the Li evaporation source is 400° C., and the film thickness is 100-200 nm.

8) Take the sample out, remove the mask in the glove box, lead out the positive and negative current collectors with Cu wires, and then still place them in the evaporation equipment to evaporate the organic protective layer. The evaporation source used is PEN particles (polyethylene 2,6-naphthalate), placed in a molybdenum boat. The vacuum degree of the evaporation chamber is 10 ⁻³ Pa, the heating temperature of the evaporation source is 300° C., and the coating thickness is 150 nm.

9) Take the battery chip out of the evaporation equipment and put it directly into the glove box. The layer structure of the lithium battery chip is shown in Figure 4. Al ₂ O ₃ thin film 401, positive and negative current collector thin film 402; positive thin film 403; LiPON solid electrolyte thin film 404; Li negative thin film 405;

Integration of lithium-ion batteries with thin-film solar cells:

Lead out the lithium battery electrode (collector) with a wire. The flexible metal substrate of the lithium battery and the organic flexible substrate of the solar cell are bonded together with EVA glue, and the boundary is filled with butyl sealant. Integrated operations, including battery wire connection and thermocompression packaging, are performed in a glove box.

The positive electrode (p junction) of the solar cell is connected to the current collector of the positive electrode _LiCoO2 of the lithium battery, and the negative electrode (n junction) is connected to the current collector of the negative electrode Li of the lithium battery, and a switch is set to control whether to charge the lithium battery. The positive and negative current collectors of the lithium battery are connected to the load through wires, and a switch is set to control whether to supply power to the load. The circuit connection method is shown in Figure 5.

The III-V solar cells are laser cut into small pieces and packaged in series and parallel to obtain the required output voltage of 4V-5V. The measured IV curves of the series and parallel battery arrays are shown in Figure 8: the short-circuit current is about 16mA, and the open-circuit voltage is about 4.1V, which can meet the charging needs of lithium batteries. The irradiance in the test is 1000W/m ² , and the sunlight spectrum is AM1.5.

A layer of aluminum-plastic film is hot-pressed outside the PEN protective film layer of the lithium battery. The thickness of the aluminum-plastic film is about 120μm-150μm, the water vapor transmission rate<10 ^-4 g/m ² ·d.1atm; the oxygen transmission rate<0.1cm ³ /m ² ·d.1atm;

The charging and discharging curves of the lithium battery are shown in Figure 6 and Figure 7, the charging voltage is 4.1V, and the maximum capacity of the battery is 20mAh after 1 hour.

The integrated energy supply product is the integration of III and V thin-film solar cells and all-solid-state thin-film lithium batteries. The positive electrode of the solar cell is connected to the positive electrode current collector of the lithium battery, and the negative electrode of the solar cell is connected to the current collector of the negative electrode Li of the lithium battery; The battery is provided with a flexible substrate, and the solar cell is provided with an organic flexible substrate. The flexible substrate of the lithium battery and the organic flexible substrate of the solar cell are bonded together by mechanical thermocompression with hot melt adhesive. From the organic flexible substrate upward, the battery is followed by back metal, bottom battery InGaAs, buffer layer InAlGaAs, tunnel junction AlGaAs, top battery GaInP, window layer AlInP, front electrode, anti-reflection film and front barrier film. The positive and negative current collectors of the lithium battery are respectively led out by wires for connecting the load.

Example 2

Preparation of triple-five double-junction batteries:

Step 1. Use Ge substrate to reduce cost. Using MOCVD (Metal Organic Chemical Vapor Deposition) method to epitaxially grow sacrificial layer, buffer layer, emitter layer, _tunnel junction, window layer, etc. on the substrate in sequence. Phosphine (PH ₃ ), two of the gases such as trimethylaluminum (TMAl), trimethylgallium (TMGa), and trimethylindium (TMIn). Tetrabromomethane (CBr ₄ ) and H ₂ S were used for doping.

In the epitaxial layer structure, the thickness of the substrate is 160 μm, the thickness of the sacrificial layer is 80 nm; the thickness of the n-type Al _0.3 In _0.7 P window layer is 50 nm, and the doping concentration is 1×10 ¹⁹ cm ^-3 ; the n-type Ga _0.5 In _0.5 P emits Region, thickness 50nm, p-type Ga _0.5 In _0.5 P base region, thickness 50nm, p-type Ga _0.5 In _0.5 P tunnel junction, thickness 30nm, n-type Al _0.1 Ga _0.9 As tunnel junction thickness 50nm, n-type In _x Al _y Ga _z As buffer layer, 0≤x≤0.3, 0≤y≤0.1, 0.7≤z≤0.9, thickness is 300nm, n-type In _0.3 Ga _0.7 As bottom cell emitter thickness is 100-nm, bottom cell base Thickness is

100nm, p-type In _0.3 Ga _0.7 As back field thickness is 100nm.

Step 2. The back metal Ag is deposited on the epitaxial layer by magnetron sputtering.

Step 5. Using Ni metal material on the front side of the solar cell to prepare the front electrode.

6. Deposit a layer of _TiO2 anti-reflection film on the front of the solar cell by magnetron sputtering.

Other operations are the same as in Example 1.

The flexible thin-film III-V solar cell has a photoelectric conversion efficiency of up to 29%. Embodiment 3 Preparation of all-solid-state thin-film lithium battery

In this embodiment, in Step 1, a layer of SiO ₂ film with a thickness of 100 nm is plated on the copper foil.

In step 3, LiMn ₂ O ₄ is selected for the magnetron sputtering chamber, and the deposition thickness is 80 nm to form the positive electrode of the lithium battery. After the deposition, the sample stage was heated to 400°C-500°C, and annealed for about 15 minutes to obtain a film with uniform grain size, and then cooled naturally.

In step 5, the thickness of the LiPON electrolyte film is 100nm.

Other operations are the same as in Example 1.

The invention adopts the integrated integration of thin-film solar cells and thin-film lithium batteries to realize the softness, bendability and portability of the batteries, so that electronic products can be made lighter. The third and fifth group thin-film battery that the present invention adopts, the substrate is flexible PET or PEN material, and the overall thickness of the solar cell is below 200 microns; The thin-film lithium battery substrate that adopts among the present invention is a metal foil, and the substrate thickness is 50 -100μm, the overall thickness of the lithium battery can be controlled within 300μm, combined with solar energy, EVA glue is used for hot pressing, the thickness of the entire mobile power product is between 0.8-1mm, and it is flexible. This integrated battery is greatly reduced in weight and volume compared with the currently commonly used lithium batteries, so it can greatly reduce the weight and volume of electronic products. If it can be combined with flexible circuits and flexible displays, the entire electronic product can be made flexible and thin. , foldable and portable, etc., bring great convenience to people's life and work.

The above embodiments are only descriptions of preferred implementations of the present invention, and are not intended to limit the scope of the present invention. Without departing from the design spirit of the present invention, ordinary engineers and technicians in the field may make various modifications to the technical solutions of the present invention. and improvements, all should fall within the scope of protection determined by the claims of the present invention.

Claims (10)

1. An integrated energy supply product, characterized in that it is an integration of III-V thin-film solar cells and all-solid-state thin-film lithium batteries, the positive electrode of the solar cell is connected to the positive electrode current collector of the lithium battery, and the negative electrode of the solar cell is connected to the lithium battery. The current collector of the negative electrode Li of the battery; The lithium battery is provided with a flexible metal foil substrate, the solar cell is provided with an organic flexible substrate, and the flexible substrate of the lithium battery and the organic flexible substrate of the solar cell are bonded together by mechanical thermocompression with hot melt adhesive; The positive and negative current collectors of the lithium battery are respectively led out by wires for connecting the load. 2. The energy supply product according to claim 1, characterized in that, from the organic flexible substrate upwards, the group III and V thin-film solar cells are successively the back metal with a thickness of 30-50 nm, and the bottom cell InGaAs with a thickness of 150-200 nm. , the buffer layer InAlGaAs with a thickness of 100-300nm, the tunnel junction AlGaAs with a thickness of 20-80nm, the top cell GaInP with a thickness of 100-200nm, the AlInP window layer with a thickness of 30-50nm, the front electrode with a thickness of 20-50nm, and the antireflection with a thickness of 20-50nm Film, front barrier film with a thickness of 50-80 μm. 3. The energy supply product according to claim 2, characterized in that, in the III-V thin-film solar cell, the window layer is n-type Al _0.3 In _0.7 P, and the doping concentration is (0.5-2)×10 ¹⁹ cm ^-3 ; the emitter region is n-type Ga _0.5 In _0.5 P, doping concentration (0.5-2)×10 ¹⁸ cm ^-3 ; the base region is p-type Ga _0.5 In _0.5 P, doping concentration (0.5-2)× 10 ¹⁸ cm ^-3 ; the tunnel junction is a p-type Ga _0.5 In _0.5 tunnel junction and an n-type Al _0.1 Ga _0.9 As tunnel junction, and the doping concentrations of the two tunnel junctions are independently (1-5)×10 ¹⁹ cm ^-3 ; the buffer layer is n-type In _{x AlyGaz} As, 0≤x≤0.3, 0≤y≤0.1 _, 0.7≤z≤0.9, doping concentration (0.5-2)×10 ¹⁷ cm ^-3 ; bottom The emission region of the cell is n-type In _0.3 Ga _0.7 As, the thickness is 100-200nm, and the doping concentration is 1×10 ¹⁸ cm ^-3 ; the base region of the bottom cell is p-type In _0.3 Ga _0.7 As, and the doping concentration is (0.5-2 )×10 ¹⁸ cm ^-3 ; the back field is p-type In _0.3 Ga _0.7 As, and the doping concentration is (1-5)×10 ¹⁹ cm ^-3 . 4. The energy supply product according to claim 1, wherein an anti-reflection film is deposited on the front of the III-V thin-film solar cell, and the material of the anti-reflection film is ITO, AZO, TiO ₂ , SiO ₂ One or more of them; the anti-reflection film is packaged with a transparent waterproof film, and the material of the transparent waterproof film is ETFE. 5. The energy supply product according to claim 1, wherein the positive pole of the lithium battery is LiCoO ₂ or LiMn ₂ O ₄ , the electrolyte is a LiPON solid electrolyte, and the negative pole is lithium metal; the positive pole, negative pole, The electrolyte and the current collector are respectively made by magnetron sputtering and/or evaporation; the thickness of the positive electrode is 20-100nm, the thickness of the electrolyte is 100-200nm, and the thickness of the negative electrode is 100-200nm. 6. The energy supply product according to claim 1, wherein the positive and negative current collectors of the lithium battery are integrated through magnetron sputtering with a mask, and the thickness of the current collector is 50-200nm. 7. The preparation method of the integrated energy supply product described in any one of claims 1-6, characterized in that, comprising the preparation of III-V thin-film solar cells, the preparation of all-solid-state thin-film lithium batteries, and the use of hot-melt The all-solid-state lithium-ion battery and the thin-film solar battery are integrated by glue mechanical thermocompression bonding. 8. the preparation method according to claim 7, is characterized in that, the preparation method of described III-V thin-film solar cell is: S1: cleaning and drying the semiconductor substrate; the semiconductor substrate is a GaAs substrate or a Ge substrate; S2: The sacrificial layer, buffer layer, emitter layer, tunnel junction, and window layer are epitaxially grown on the substrate in sequence by MOCVD method. The reaction precursor gas introduced in the MOCVD process is arsine, phosphine, trimethylaluminum, and trimethylaluminum. Two or more of gallium-based and trimethylindium; S3: The back metal is deposited on the epitaxial layer by magnetron sputtering, and a layer of flexible waterproof material is hot-pressed on the back metal as the transfer substrate of the epitaxial layer; S4: peeling off the epitaxial layer from the substrate; S5: Prepare the front electrode on the front side of the solar cell by screen printing; S6: Deposit an anti-reflection film on the front of the solar cell by magnetron sputtering. 9. The preparation method according to claim 8, characterized in that, the preparation method of the all-solid-state thin-film lithium battery is: 1) Coating an insulating layer of Al ₂ O ₃ or SiO ₂ on the metal foil by magnetron sputtering, the material of the metal foil is stainless steel, copper or silver; 2) Use the positive and negative current collector shape masks, positive electrode shape masks, and electrolyte shape masks successively, and use magnetron sputtering to make positive and negative electrode current collectors, positive electrodes, and electrolytes; 3) Remove the electrolyte mask, place a mask in the shape of the negative electrode, and vapor-deposit the negative electrode; then remove the negative electrode mask, and vapor-deposit the organic protective layer, using PEN particles as the evaporation source. 10. An equipment for preparing the integrated energy supply product according to any one of claims 1-6, characterized in that the equipment comprises a glove box, and magnetron sputtering is integrated in the glove box Coating equipment, vacuum evaporation equipment and hot pressing equipment, the hot pressing equipment is used for the overall integration of solar cell waterproof packaging, lithium battery waterproof packaging, lithium battery and solar energy.