CN115621479A - Thermal battery intermediate layer and preparation method thereof - Google Patents
Thermal battery intermediate layer and preparation method thereof Download PDFInfo
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- CN115621479A CN115621479A CN202111594886.3A CN202111594886A CN115621479A CN 115621479 A CN115621479 A CN 115621479A CN 202111594886 A CN202111594886 A CN 202111594886A CN 115621479 A CN115621479 A CN 115621479A
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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
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- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to the field of thermal batteries, in particular to a thermal battery intermediate layer and a preparation method thereof.
Description
Technical Field
The invention relates to the field of thermal batteries, in particular to a thermal battery interlayer and a preparation method thereof.
Background
Advances in military weapons systems (e.g., hypersonic cruise missiles) have led to the development of thermal batteries with high energy density and power output.
However, the transition metal sulfides of thermal batteries produce intermediate reaction products such as polysulfides when operated at high temperatures for long periods of time with small currents, and the formation of polysulfides is accompanied by self-discharge effects with the negative electrode, resulting in irreversible loss of capacity. Binary sulfide Ni proposed in ACS appl. Mater. Interfaces 2020,12 (45), 50377-50387 1-x Co x S 2 The technology better limits the 'shuttle' of polysulfide from a positive electrode to a negative electrode, but according to the actual discharge result, the binary sulfide is at 600 mA-cm -2 The actual output capacity is more than 100mA cm -2 The performance of the binary sulfide is further improved.
The transition metal halide has high potential characteristics (monomer > 2.5V). However, the highly conductive Ni-NiCl proposed by documents Mater. Lett.2021,301,130272. And J.electrochem.Soc.2019,166 (15), A3599-A3605 2 And FeF 3 None of the MWCNTs (> 3.3V) materials are effective for long periods of time because the "shuttling effect" caused by the dissolution of the halide positive electrode material in the halide-containing molten salt electrolyte (e.g. LiCl, liF) is more severe. Similarly, oxide materials also suffer from similar problems at high temperatures.
Based on the energy technology 2020,8 (12), 2000737, it was found that thin electrodes, although reducing polarization, do not overcome the "shuttle effect".
In the previous work for improving the performance of the thermal battery, the invention CN 108963291B discloses a thin thermal battery with an electrode system and a heating system independent, which comprises the electrode system and the heating system, and is characterized in that: the heating system is wrapped by the heat conducting insulating layer and supplies heat to the electrode system from the periphery; the heating system is an ignition system consisting of a mixture of zirconium and barium chromate and an electric ignition head, and meanwhile, a combustion system consisting of a mixture of iron and potassium perchlorate is filled in the heat-conducting insulating layer; the preparation method of the electrode system is a pressing method or a thermal spraying method; the describedThe pressing method comprises the steps that the positive electrode material, the diaphragm material, the negative electrode material and the current collector are respectively pressed into tablets in a cold pressing mode, and then the positive electrode material, the diaphragm material, the negative electrode material and the current collector are sequentially stacked up and down to form a single battery structure, and the single battery structures are stacked to form an electrode system; the thermal spraying method comprises the steps of pressing a negative electrode material into sheets, spraying a positive electrode material on one surface of a current collector, spraying a diaphragm material on the positive electrode material, and finally, stacking the negative electrode material sheets under the diaphragm material to form a single battery structure, wherein the single battery structure is stacked to form an electrode system; the active material of the anode material is an alloy compound Fe x Co 1-x S 2 、Fe x Ni 1-x S 2 、 Co x Ni 1-x S 2 Or Fe x Co y Ni 1-xy S 2 Wherein x is more than 0 and less than 1, x and y are more than 0 and less than 1, and the product is pure; the shape of the electrode system is a solid column or a hollow column; the heat conducting insulating layer is made of a composite material which is composed of one or more of beryllium oxide, aluminum nitride, boron nitride or silicon nitride, has the heat conductivity of 32-400W/(m.K), the resistivity of more than 1015 omega.cm and the melting point of more than 1200 ℃; the thermally conductive insulation layer separates the battery heating system from the electrode system.
The invention CN111403731B discloses a 3d orbital alloy sulfide material, and the chemical formula of the 3d orbital alloy sulfide material is Fe 0.5 Co x Ni y S 2 Wherein 0 < x < 0.3, x + y = 0.5, which exhibits a hollowed "raspberry" -like structure, the 3d orbital alloy sulfide being a single phase material.
The invention CN111244425B discloses a positive electrode material for a monomer 4V-grade thermal battery, which comprises the following materials in percentage by mass: 50-85% of monomer 4V-grade active positive electrode material, 10-30% of ultrahigh-pressure molten salt electrolyte, 6-10% of high-voltage stabilizer and 0.1-5% of high-conductivity conductive agent; the electrochemical stability window of the ultrahigh-pressure molten salt electrolyte is more than 4.5V, and the eutectic melting point is 420-450 ℃.
The invention CN111969140B discloses a high-strength steel wire ropeThe high-specific-performance thermal battery consists of a shell, a neural network heat-insulating layer, an insulating layer and a mixed electrode layer from outside to inside; the shell is made of one of stainless steel, titanium alloy and aluminum magnesium alloy; the insulating layer is made of one or more of aluminum silicate fiber felt, asbestos sheets, min-K materials, ceramic membranes, aerogel or mica sheets; the neural network heat-insulating layer is formed by alternately laminating a composite phase-change material and a uniform heating material, and the composite phase-change material and the uniform heating material form a progressive energy storage structure; the dosage of the uniform heating material is more than 1.1 times of the dosage of the composite phase-change material; the mixed electrode layer consists of a uniform heating material, a current collector, a high-specific-capacity positive electrode material, a diaphragm and a negative electrode in sequence from top to bottom in space to form a laminated structure; the active material of the high-specific-capacity anode material is any one of a local single crystal compound or Ru-doped 3d orbital alloy sulfide; the local single crystal compound has a specific chemical formula of Ni 1-x Co x S 2 X is more than 0.2; the Ni 1-x Co x S 2 The material is formed by nano sheets into microspheres, the thickness of the nano sheet structure is less than 30nm, co is only +2 valence, and Ni exists +2 and +3 valence at the same time; the total usage of the uniform heating material is less than 26 percent of the total mass of the complete battery in percentage by weight; the preparation method of the uniform heating material comprises the following steps: pouring analytically pure potassium perchlorate into a high-energy ball mill cup, adding water to prepare a slurry, adding zirconia balls, setting the rotating speed to be more than 3000r/min for high-energy ball milling, wherein the high-energy ball milling time is 30-2 min, then stopping running, cooling for more than 10min, then running the high-energy ball mill, repeating the steps, wherein the high-energy ball milling runs for 4-6 h, then putting the ball-milled powder into a freeze dryer, running the freeze dryer to remove excessive water through sublimation, crushing by using a crusher to at least pass through a 400-mesh sieve to obtain superfine potassium perchlorate, and mixing active iron powder and inorganic sylvite in an inert atmosphere glove box to form potassium-containing iron powder; finally, mixing the superfine potassium perchlorate and the potassium-containing iron powder in any physical or chemical way to obtain the uniform heating material; the physical means is to apply the living thingsPutting the sexual iron powder and the inorganic potassium salt into a closed ball milling tank for ball milling and mixing; the chemical method is that the active iron powder and the inorganic sylvite are put into an absolute ethyl alcohol solvent for mixing, and then the mixture is heated at 80 ℃ in an inert atmosphere to remove the ethyl alcohol; the content of pure iron in the active iron powder is more than 90 percent; the composite phase change material comprises the following components in percentage by weight: 30-90% of phase-change molten salt, 0.1-20% of carbon material and 5-70% of carrier with porosity of 30-99%, wherein the phase-change molten salt comprises any two or three of the following components in percentage by weight: liF:5% -30% of Li 2 SO 4 :0 to 95%, liCl:0 to 95 percent; the Ru-doped 3d orbital alloy sulfide has a chemical formula of Fe 1-x-y- z Co x Ni y Ru z S 2 Wherein x + y + z is less than or equal to 0.5, the structure with a hole in the middle is presented, and the molar quantity z of the Ru doping is less than 0.1.
The invention CN111313019B discloses a high-voltage anode material with ultrahigh power output for a thermal battery, which is characterized in that the anode material is prepared from the following materials in percentage by mass: non-stoichiometric ratio Ru x Fe 1-4x/3 F 3 50-85% of active material, 10-30% of high-voltage high-ionic-conductivity electrolyte, 0.1-5% of high-voltage stabilizer and 6-10% of high-conductivity conductive agent, wherein the non-stoichiometric ratio Ru is x Fe 1-4x/3 F 3 The value range of x in the active material is more than 0 and less than 0.08. The high-voltage anode material is an anode material with a monomer potential of more than 3V; the high-voltage high-ion conductivity molten salt electrolyte is LiF-LiCl-KF ternary eutectic molten salt or LiF-LiCl-NaF ternary eutectic molten salt; the high voltage stabilizer is Li 6.75 La 3 Zr 1.75 Ta 0.25 O 12 ，Li 7-3x Ga x La 3 Zr 2 O 12 ，Li 6.4 Al 0.2 La 3 Zr 2 O 12 Wherein, li is 7-3x Ga x La 3 Zr 2 O 1 Wherein the value range of x is more than 0.05 and less than 0.85; the high-conductivity conductive agent is a carbon nanotubeGraphene, acetylene black and carbon nanotube composite with equal mass ratio, and carbon nanotube and graphene composite with equal mass ratio.
The invention CN109841821B discloses a high-potential high-power type thermal battery anode material, which is characterized in that: the composite material is prepared from the following raw materials in percentage by weight: 50-95% of composite high-potential active positive electrode material, 4-49.5% of high-ionic conductivity electrolyte and 0.5-20% of high-conductivity electronic conductive agent; the composite high-potential active anode material consists of 5-95 wt% of FeF3 and 5-95 wt% of FeF2, and the preparation method is an in-situ synthesis method or a direct mixing method; the electrolyte with high ionic conductivity is LiF-NaF-LiCl or LiF-KF-LiCl eutectic molten salt.
The invention CN113193298B discloses a preparation method of an ultrathin carbon-coated membrane, which is characterized by comprising the following steps: (1) dispersing: placing a carbon source in a container, and adding a solvent A for ultrasonic dispersion; then removing the solvent A in a freeze dryer or a vacuum oven to obtain a pre-dispersed carbon source; (2) mixing materials: adding the pre-dispersed carbon source obtained in the step (1) into a stirring tank, adding an adhesive, then placing the stirring tank into a planetary stirrer, and stirring by adopting a double stirring mode to obtain mixed slurry; in the double stirring mode, firstly, the cosine gradient type rotation mode is operated to reach the set peak rotating speed of the initial cosine parameter, and then the sine gradient type revolution mode is operated to start stirring; the whole process of the double stirring mode is carried out more than once; (3) coating: pouring the mixed slurry obtained in the step (2) onto a base film, and coating the mixed slurry on the base film by adopting any one of blade coating, rotary coating and spraying to obtain a mixed film; and (4) drying: and (4) sequentially removing surface adsorbed water and solvent from the mixed membrane in the step (3) by adopting a blowing drying mode and a vacuum drying mode to obtain the ultrathin carbon-coated membrane.
The document Mater.Lett.2019,249,81-83 discloses tungsten disulfide (WS) 2 ) The nano-sheet is researched and used as a positive electrode material of a thermal battery. WS (WS) 2 The thermal stability of the composition is up to 1200 ℃. The open circuit voltage was 1.43V versus Li-B anode. At 150mA · cm -2 At a current density of (2), li-B/WS 2 The specific capacity of the single battery is 334.7 mAh.g -1 Cutoff voltage was 1.0V, and final discharge products were W and Li 2 And S. This work is further applied to WS 2 Promising positive electrode materials as long-life thermal batteries provide one starting point.
Document J.electrochem.Soc.2019,166 (15), A3599-A3605 discloses the synthesis of anhydrous FeF 3 And the applicability of the material as a positive electrode material of a thermal battery is researched. Its structure, thermal stability and electrochemical performance were also investigated. Synthetic anhydrous FeF 3 With a hierarchical structure and a decomposition threshold temperature of 800 ℃. At 100mA cm -2 At a current density of (3), li-B/FeF 3 The initial discharge voltage of the single battery is 3.20V, and the specific capacity is 81.9mAh g -1 The cut-off voltage was 2.0V. Carbon Nanotubes (MWCNTs) act as a conductive agent, resulting in a reduction of the total polarization from 45m Ω to 10m Ω. In particular, li-B/FeF 3 The initial discharge voltage of the MWCNTs single cell is 3.27V, and the specific capacity is 160.7mAh g -1 . This work was carried out to further apply FeF 3 The high voltage anode material as a high power thermal battery provides an open end.
Document Energy Technology 2020,8 (12), 2000737 discloses the successful preparation of thin film single cells by a screen printing process. A single cell with a 100 μm thin film cathode and a 200 μm thin film electrolyte by screen printing technique showed 1163.4As g -1 To a specific capacity of 1.5V. By way of comparison, a single cell powder pressing process with a 500 μm particle cathode and a 300 μm particle electrolyte exhibited only 361.3As g -1 The specific capacity of (a). The improvement of the specific capacity of the single battery prepared by the screen printing method can be attributed to the microstructure of the film, and the diffusion rate of Li & lt + & gt is improved by reducing the thickness of the single battery macroscopically, so that the maximum capacity is released. An active substance. Thin film single cells also exhibit low diffusion resistance, making it possible to adapt them to pulse miniaturized thermal cells. This work provides guidance for the potential engineering application of screen printing techniques in thermal battery preparation.
Documents ACS appl. Mater. Interfaces 2020,12 (45), 50377-50387 disclose the rapid synthesis of Co-doped NiS by hydrothermal method 2 Micro/nano structures. We have found thatDiscovery of Ni 1-x Co x S 2 The specific capacity of the micro/nano structure increases with the increase of the Co doping amount. At 100mA cm -2 At current density of (2), ni 0.5 Co 0.5 S 2 Has a specific capacity of about 1565.2As g -1 (434.8 mAh·g -1 ) The cut-off voltage was 1.5V. The pulse voltage is 2.5A cm because of the small polarization impedance (5 m omega) –2 The pulse current of (2) reaches about 1.74V,30ms. Furthermore, the discharge mechanism is proposed based on the analysis of the discharge products by anion redox chemistry. In addition, based on synthetic Ni 0.5 Co 0.5 S 2 The positive electrode material was assembled with a 3.9kg all-thermal battery. It is to be noted that the total heat cell is at 100mA cm -2 The current density discharge of (1) has a running time of about 4000s, and can realize about 142.5 Wh-kg -1 High specific energy density. In summary, this work suggests an efficient positive electrode material for thermal batteries with high specific energy and long service life.
The document mater.lett.2021,297,130007 discloses the development of a porous ceramic fiber separator substrate using mullite fibers, a ceramic fiber, using a wet-laid technique. The substrate is modified with a magnesium acetate precursor to obtain a porous, flexible, strong ceramic fiber membrane (CFS) containing nano-magnesia particles. The CFS has a diameter exceeding 11.3cm, but is relatively thin (about 0.3 mm). The application of CFS obviously improves the prior Li-B/LiF-LiCl-LiBr/FeS 2 Electrochemical performance of the electrochemical system. Li-B/LiF-LiCl-LiBr/FeS with CFS 2 The specific capacity of the battery is improved by 24 percent by an electrochemical system even if the specific capacity is 5000mA cm -2 Can also produce a polarization resistance of 0.011 omega at high current pulse densities. The results of this study indicate that CFS can effectively improve the performance of current thermal battery electrochemical systems.
The document Mater.Lett.2021,301,130272 discloses the development of reduced NiCl with Ni as a conductive agent by simple hydrogen reduction 2 . When used as a thermal battery cathode, niCl 2 The base composite material has a high peak voltage of 2.51V and a short activation time of 0.67s, and has an excellent pulse discharge capacity. This work provides a kind of forehand for high voltage cathodesAlternative scenario for guiding NiCl 2 Further application of the material.
Although the above documents have a stepwise effect in terms of long lifetime, there is still no phenomenon that the performance of the transition metal halide, sulfide, and oxide system is significantly improved and the "shuttle effect" is effectively prevented in a long-term operation mode. Therefore, in the invention, the applicant integrates the technology invented by the applicant and provides a thermal battery intermediate layer and a preparation method thereof, so that the positive and negative polarity performances of the thermal battery are improved, and a new development direction is brought to the thermal battery research.
Disclosure of Invention
The invention provides a thermal battery intermediate layer and a preparation method thereof for the first time, aiming at comprehensively improving the performance of a thermal battery transition metal sulfide, halide and oxide system.
The specific technical scheme is as follows:
the first purpose of the invention is to provide a thermal battery intermediate layer, the composition material of the thermal battery intermediate layer is any one or two of carbon material and ceramic powder or a mixed material formed by the carbon material and the ceramic powder or a solid electrolyte; the thermal battery middle layer is arranged among any relative positions of the anode, the diaphragm and the cathode, and comprises one or more of the following forms: 1) Positive electrode-intermediate layer-separator;
2) Negative electrode-intermediate layer-separator; 3) Positive electrode-separator-intermediate layer; 4) Negative electrode-separator-intermediate layer;
5) Membrane-intermediate layer-membrane.
Preferably, the intermediate layer of the thermal battery can be arranged and assembled in various ways in the thermal battery.
Preferably, the membrane-intermediate layer-membrane may be repeatedly installed in the same cell thermal battery for a plurality of times.
Preferably, the material composition of the thermal battery middle layer is not changed within the thermal battery working temperature range of 200-800 ℃.
The intermediate layer of the thermal battery is any one of the following: the composite electrode comprises a carbon material layer, a ceramic powder layer, a composite layer of a carbon material and a solid electrolyte, a composite layer of a carbon material and a ceramic powder, a composite layer of a ceramic powder and a solid electrolyte, and a composite layer of a carbon material, a solid electrolyte and a ceramic powder.
Preferably, the mass percentage of the carbon material in the intermediate layer of the thermal battery is 0-100%, the mass percentage of the solid electrolyte is 0-99.9%, and the mass percentage of the ceramic powder is 0-100%.
Preferably, the thermal battery intermediate layer does not obstruct ion transport and has a characteristic of accelerating electron transport.
Preferably, the carbon material is any one or more of activated carbon, graphite, carbon nanotubes, graphene, acetylene black, ketjen black, graphdiyne and fullerene.
Preferably, the thickness of the thermal battery middle layer is 1-500 μm.
Preferably, the area specific mass of the thermal battery middle layer is 0.1mg/cm 2 ～150mg/cm 2 。
Preferably, the diaphragm is a pressed diaphragm or a sprayed diaphragm or a ceramic fiber diaphragm.
Preferably, the ceramic fiber diaphragm is prepared from mullite fiber by adopting a wet papermaking technology; the mullite fiber is a mixture of alumina and aluminum silicate.
Preferably, the ceramic fiber separator is covered with nano-MgO particles.
Preferably, the solid electrolyte comprises Li 6.75 La 3 Zr 1.75 Ta 0.25 O 12 ， Li 7-3x Ga x La 3 Zr 2 O 12 ，Li 6.4 Al 0.2 La 3 Zr 2 O 12 ，Li 7 La 3 Zr 2 O 12 ，Li 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 Wherein, li is 7-3x Ga x La 3 Zr 2 O 12 Wherein the value range of x is more than 0.05 and less than 0.85.
The ceramic powder is a non-stoichiometric material or a mixed material of the non-stoichiometric material and other compounds, and the non-stoichiometric materialThe material is TiO 2-x 、ZrO 2-x Either one or both.
The other compounds are any one or more of beryllium oxide, aluminum silicate, aluminum nitride, boron nitride, silicon nitride, titanium dioxide, magnesium oxide and vanadium pentoxide.
The second purpose of the invention is to provide a preparation method of the thermal battery intermediate layer, which is characterized in that the intermediate layer is prepared by uniformly mixing the component materials of the intermediate layer and then performing any one of a tabletting stacking method and a coating stacking method.
The tabletting stacking method is to adopt any one of cold pressing or hot pressing of the thermal battery interlayer material by a pressing machine to prepare an interlayer sheet for installation.
The coating stacking method is that the intermediate layer material of the thermal battery is directly coated on the base film to become the intermediate layer and then is installed; the basement membrane is any one of commercial pp diaphragm, pe diaphragm, cellulose acetate diaphragm or ceramic fibre diaphragm.
Preferably, the direct coating comprises the steps of:
(1) Dispersing: weighing the constituent materials of the thermal battery middle layer, placing the constituent materials in a container, and adding a solvent for ultrasonic dispersion; then removing the solvent in a freeze dryer or a vacuum oven to obtain a pre-dispersion coating source;
(2) Mixing materials: adding the pre-dispersion coating source obtained in the step (1) into a stirring tank, adding an adhesive, then placing the stirring tank into a planetary stirrer, and stirring by adopting a dual stirring mode to obtain mixed slurry; in the double stirring mode, firstly, the cosine gradient type rotation mode is operated to reach the set peak rotating speed of the initial cosine parameter, and then the sine gradient type revolution mode is operated to start stirring; the whole process of the double stirring mode is carried out more than once;
(3) Coating: pouring the mixed slurry obtained in the step (2) onto a base film, and coating the mixed slurry on the base film by adopting any one of blade coating, rotary coating and spraying to obtain a mixed film;
(4) And (3) drying: and (4) sequentially removing surface adsorbed water and a solvent from the mixed membrane in the step (3) by adopting a blowing drying mode and a vacuum drying mode, and heating the mixed membrane for more than 1h in an environment with the temperature of not less than 400 ℃ to obtain the ultrathin carbon-coated membrane.
Preferably, the thermal battery interlayer is applied to the preparation of a thermal battery.
The principle of the invention is as follows: the inventor works in Mater.Lett.2021,297,130007. And finds that the FeS serving as the anode material of the traditional thermal battery can be greatly improved by optimizing the diaphragm 2 And the capacity output is realized when the high-temperature operation is carried out for a long time under a small current. Based on this phenomenon, researchers believe that the technical pattern of the existing thermal battery will be changed if the nonpolar ceramic fiber membrane is further optimized to be a multifunctional membrane capable of adsorbing and blocking substances such as "polysulfide", "polyhalide", and the like. This optimization approach is equally applicable to oxide cathode systems.
Therefore, the invention further applies the carbon-coated diaphragm technology to the thermal battery on the basis of the prior art CN113193298B, and simultaneously, according to the characteristics of the middle layer of the carbon layer, the mixed layer adopting the solid electrolyte and the ceramic powder can also play roles in ion conduction and preventing the 'shuttle effect' of polysulfide and poly halide at high temperature.
Most importantly, the invention firstly proposes to use non-stoichiometric oxide material TiO 2-x ， ZrO 2-x The functional material is introduced into the thermal battery to be used as a functional material which does not participate in the electrochemical reaction of the thermal battery, mainly utilizes the positive charge characteristic of the oxygen vacancy, adsorbs polysulfide and polyhalide of surface negative charge at high temperature, and in addition, the oxygen vacancy can capture unpaired electrons, so that the concentration of electron carriers at an increased interface is effectively increased, and the electrical conductivity is enhanced.
In order to ensure that the carbon material can be effectively dispersed in a solid without agglomeration and increase the formability in a tabletting manufacturing mode, the carbon material is mixed with a solid electrolyte and/or a ceramic component to effectively ensure the structural function integration of the intermediate layer. The applicant has a more mature carbon material/solid electrolyte mixing experience in the granted inventions CN111313019B and CN111244425B, and in the present invention it was first proposed to apply it as an intermediate layer on a separator material. Therefore, the intermediate layer can not hinder the shuttle effect and the transmission of the molten salt of lithium ions at high temperature.
Has the advantages that:
1. the concept of 'intermediate layer' is put forward in the thermal battery for the first time, the intermediate layer which is used for blocking the intermediate reaction product of the sulfide, the halide and the oxide of the thermal battery is introduced, the utilization rate of the anode material can be obviously improved on the premise of not increasing the weight of the battery, and the specific energy of the thermal battery is further improved.
2. The carbon material or ceramic powder is used as an adsorption blocking agent for blocking an intermediate product generated by self-discharge of the positive electrode of the thermal battery for the first time, and a solid electrolyte is introduced to improve the ion conduction characteristic of the intermediate layer.
3. The ceramic powder can reduce the agglomeration of the nano carbon material and improve the formability of the pole piece prepared by a tabletting method, and part of the ceramic powder (such as TiO) 2-x ，ZrO 2-x ) Can also be used as an adsorbent to prevent the shuttle effect of the self-discharge intermediate product of the anode of the thermal battery. The present invention is also the first successful application of non-stoichiometric oxides in thermal batteries.
4. The 'middle layer' proposed by the invention is orderly and independently layered on the assembly space, and is not directly mixed with the diaphragm material. Thereby breaking the three-layer electrode layer structure of 'anode-diaphragm-cathode' limited by the existing thermal battery assembly no matter the spraying method or the tabletting method. The assembling mode of the composite material is changed into a novel assembling structure of a positive electrode-middle layer-diaphragm-negative electrode, or a negative electrode-middle layer-diaphragm-positive electrode four-layer structure, or a positive electrode-middle layer-diaphragm-middle layer-negative electrode five-layer structure, or a (diaphragm-middle layer-diaphragm) x N layer, wherein N is more than or equal to 1.
5. The intermediate layer provided by the invention is simple to assemble and strong in operability, and the specific energy of the thermal battery in long-time operation can be obviously improved on the premise of not increasing the weight of the battery by only selecting the related materials provided by the invention.
Drawings
FIG. 1 is a schematic diagram of several exemplary structures of intermediate layers of a thermal battery of the present invention;
FIG. 2 is a SEM cross-sectional view of an intermediate layer of a thermal battery in example 5 of the present invention;
FIG. 3 shows Ni-NiCl of application example 1 and comparative example 1 of the present invention 2 The positive thermal battery works for 1 h;
FIG. 4 shows Ni in application example 2 of the present invention and comparative example 2 0.5 Co 0.5 S 2 The positive thermal battery works for a discharge curve of 2 hours;
FIG. 5 shows MnF of application example 3 of the present invention and comparative example 3 3 The positive thermal battery works for 1 h;
FIG. 6 shows FeF of application example 4 of the present invention and comparative example 4 3 -FeF 2 And the positive thermal battery works for 1 h.
Detailed Description
The following is a detailed description of the embodiments of the present invention, but the present invention is not limited to these embodiments, and any modifications or substitutions in the basic spirit of the embodiments are included in the scope of the present invention as claimed in the claims.
Example 1
A preparation method of a thermal battery interlayer comprises the following steps:
1) Selecting materials: using carbon nanotubes as carbon material, tiO 2-x As ceramic powders, li 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 Is a solid electrolyte;
2) Preparing materials: according to the mass percentage, 27.3 percent of carbon material, 48.6 percent of ceramic powder and 24.1 percent of solid electrolyte are weighed for standby;
3) Preparation: mixing carbon material, ceramic powder and solid electrolyte uniformly in a planetary stirrer, and cold pressing to obtain the final product with thickness of 100 μm and area ratio of 22mg/cm 2 The sheet of (2) is the intermediate layer of the thermal battery.
Example 2
A preparation method of a thermal battery interlayer comprises the following steps:
1) Selecting materials: with ZrO 2-x Making ceramic powder;
2) Preparing materials: weighing the ceramic powder according to the mass percentage of 100% for later use;
3) Preparation: prepared into the product with the thickness of 100 mu m and the area specific mass of 15mg/cm by adopting a cold pressing mode 2 The sheet of (2) is the intermediate layer of the thermal battery.
Example 3
A preparation method of a thermal battery interlayer comprises the following steps:
1) Selecting materials: with TiO 2-x Making ceramic powder;
2) Preparing materials: weighing the ceramic powder according to the mass percentage of 100% for later use;
3) Manufacturing: prepared into the product with the thickness of 100 mu m and the area ratio mass of 17.2mg/cm by adopting a cold pressing mode 2 The thermal battery middle layer is the thermal battery middle layer.
Example 4
A preparation method of a thermal battery interlayer comprises the following steps:
1) Selecting materials: using graphene as the carbon material, zrO 2-x As ceramic powders, li 6.75 La 3 Zr 1.75 Ta 0.25 O 12 Is a solid electrolyte;
2) Preparing materials: according to the mass percentage, the carbon material, the ceramic powder and the solid electrolyte are weighed for later use according to the carbon material proportion of 10.9 percent, the ceramic powder proportion of 66.2 percent and the solid electrolyte proportion of 22.9 percent;
3) Preparation: after carbon materials, ceramic powder and solid electrolyte are uniformly mixed in a planetary stirrer, the mixture is prepared into a mixture with the thickness of 200 mu m and the area ratio mass of 30mg/cm by adopting a cold pressing mode 2 The sheet of (2) is the intermediate layer of the thermal battery.
Example 5
A preparation method of a thermal battery interlayer comprises the following steps:
1) Selecting materials: using carbon nanotubes and SuperP as mixed carbon material, tiO 2-x As ceramic powders, li 6.75 La 3 Zr 1.75 Ta 0.25 O 12 Is a solid electrolyte;
2) Preparing materials: according to the mass percentage, the carbon material accounts for 78 percent, and TiO 2-x Weighing carbon materials, ceramic powder and solid electrolyte for later use, wherein the ceramic powder accounts for 10% and the solid electrolyte accounts for 12%;
3) Preparation: the carbon material, the ceramic powder and the solid electrolyte are uniformly mixed by adopting a gradient resonance mixing mode of CN113193298B, and then coated on a ceramic fiber diaphragm base material of documents Mater, lett, 2021,297 and 130007, wherein the coating thickness is 20 mu m, and the area ratio mass is 0.2mg/cm 2 Heating at 400 deg.C for 2h to obtain intermediate layer of thermal battery; the cross-sectional test image is shown in figure 2.
Application example 1
The thermal battery interlayer of example 1 was used as Ni-NiCl in Mater. Lett.2021,301,130272 2 The anode is LiF-LiBr-KBr/MgO, the separator is LiB, and the cathode is LiB; placing the intermediate layer between the diaphragm and the anode material, assembling 28V grade thermal battery at 100 mA-cm -2 Discharging, wherein the effective working time of the anode is 2999s, and the specific capacity of the anode is 928As/g; the discharge curve is shown in figure 3.
Application example 2
Ni of ACS appl. Mater. Interfaces 2020,12 (45), 50377-50387 using the thermal battery interlayer of example 1 0.5 Co 0.5 S 2 The anode is LiCl-LiBr-LiF/MgO as a diaphragm, and the cathode is LiB; placing the intermediate layer between the separator and the cathode material, assembling 28V grade thermal battery, and heating at 50 mA-cm -2 Discharging, wherein the effective working time of the anode is 8019s, and the specific capacity of the anode is 1582As/g; the discharge curve is shown in figure 4.
Application example 3
The intermediate layer of the thermal battery of example 2 was used as MnF of CN111244425B 3 Is a positive electrode, liF-NaF-KF-Li 2 SO 4 the/MgO is a diaphragm, and the LiB is a negative electrode; placing the intermediate layer between the diaphragm and the anode material, assembling 56V grade thermal battery at 100 mA-cm -2 Discharging, wherein the effective working time of the anode is 3610s, and the specific capacity of the anode is 1120As/g; the discharge curve is shown in figure 5.
Application example 4
FeF from CN109841821B using the interlayer of the thermal battery of example 5 3 -FeF 2 As positive electrode, in the document mater. Lett.2021,297,130007 as a substrate to form a LiCl-LiF-KF/ceramic fiber diaphragm, and LiB as a cathode. Placing the middle layer between the diaphragm and the diaphragm, assembling 56V-grade thermal battery, and measuring the current density at 100 mA-cm -2 Discharging, wherein the effective working time of the anode is 3720s, and the specific capacity of the anode is 1300As/g; the discharge curve is shown in figure 6.
Comparative example 1
Adopts a traditional thermal battery cell structure and adopts Ni-NiCl of Mater.Lett.2021,301,130272 2 A 28V-level thermal battery is assembled by taking LiF-LiBr-KBr/MgO as an anode, liB as a cathode and 100 mA.cm -2 Discharging, wherein the effective working time of the anode is 853.5s, and the specific capacity of the anode is 264As/g; the discharge curve is shown in fig. 3.
Comparative example 2
Adopts a traditional thermal battery cell structure and adopts Ni of documents ACS appl. Mater. Interfaces 2020,12 (45) and 50377-50387 0.5 Co 0.5 S 2 The anode is LiCl-LiBr-LiF/MgO as a diaphragm, and the cathode is LiB; assembling 28V grade thermal battery at 50mA cm -2 Discharging, wherein the effective working time of the anode is 7001s, and the specific capacity of the anode is 1380As/g; the discharge curve is shown in fig. 4.
Comparative example 3
A conventional thermal battery cell structure is employed. MnF of invention CN111244425B 3 Is a positive electrode, liF-NaF-KF-Li 2 SO 4 the/MgO is a diaphragm, and the LiB is a negative electrode. Assembling a 56V grade thermal battery at 100mA cm -2 Discharging, wherein the effective working time of the anode is 3157s, and the specific capacity of the anode is 979As/g; the discharge curve is shown in figure 5.
Comparative example 4
A conventional thermal battery cell structure is employed. To authorize the invention of FeF of CN109841821B 3 -FeF 2 As the anode, a ceramic fiber diaphragm of the document Mater.Lett.2021,297 and 130007 is used as a base material to form a LiCl-LiF-KF/ceramic fiber diaphragm, and LiB is used as the cathode; assembling a 56V grade thermal battery at 100mA cm -2 Discharging, wherein the effective working time of the anode is 2617s, and the specific capacity of the anode is 914.5As/g; the discharge curve is shown in figure 6.
In conclusion, the thermal battery interlayer structure and the thermal battery interlayer composition disclosed by the invention not only develop a new thermal battery research direction, but also are simple to assemble, and the actual discharge specific energy of all current thermal battery systems is obviously improved. Has extremely high engineering application value.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Claims (10)
1. The thermal battery intermediate layer is characterized in that the thermal battery intermediate layer is made of any one or two of carbon materials and ceramic powder or a mixed material of the carbon materials and solid electrolyte; the thermal battery middle layer is arranged among the positive electrode, the diaphragm and the negative electrode at any relative position, and comprises one or more of the following forms: 1) Positive electrode-intermediate layer-separator; 2) Negative electrode-intermediate layer-separator; 3) Positive electrode-separator-intermediate layer; 4) Negative electrode-separator-intermediate layer; 5) Membrane-intermediate layer-membrane;
the diaphragm-intermediate layer-diaphragm can be repeatedly installed in the same monomer thermal battery for multiple times.
The middle layer of the thermal battery is in the working temperature range of the thermal battery of 200-800 ℃, and the material composition of the middle layer is not changed.
2. The interlayer for a thermal battery of claim 1, wherein the interlayer for a thermal battery is any one of: the composite electrode comprises a carbon material layer, a ceramic powder layer, a composite layer of a carbon material and a solid electrolyte, a composite layer of a carbon material and a ceramic powder, a composite layer of a ceramic powder and a solid electrolyte, and a composite layer of a carbon material, a solid electrolyte and a ceramic powder.
3. The interlayer for a thermal battery of claim 1, wherein the interlayer for a thermal battery has a thickness of 1 μm to 500 μm.
4. The thermal battery interlayer of claim 1, wherein the thermal battery interlayer has an area specific mass of 0.1mg/cm 2 ～150mg/cm 2 。
5. The interlayer of a thermal battery of claim 1, wherein said solid electrolyte is Li 6.75 La 3 Zr 1.75 Ta 0.25 O 12 ，Li 7-3x Ga x La 3 Zr 2 O 12 ，Li 6.4 Al 0.2 La 3 Zr 2 O 12 ，Li 7 La 3 Zr 2 O 12 ，Li 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 Wherein, li is 7-3x Ga x La 3 Zr 2 O 12 Wherein the value range of x is more than 0.05 and less than 0.85.
6. The interlayer of claim 1, wherein the ceramic powder is a non-stoichiometric material or a mixture of a non-stoichiometric material and other compounds, and the non-stoichiometric material is TiO 2-x 、ZrO 2-x Either one or both.
7. The thermal battery interlayer of claim 6, wherein the other compound is any one or more of beryllium oxide, aluminum silicate, aluminum nitride, boron nitride, silicon nitride, titanium dioxide, magnesium oxide, and vanadium pentoxide.
8. The intermediate layer of a thermal battery as claimed in claim 1, wherein the carbon material is any one or more of activated carbon, graphite, carbon nanotube, graphene, acetylene black, ketjen black, graphdine, and fullerene.
9. The method for preparing the intermediate layer of the thermal battery as claimed in claim 1, wherein the intermediate layer of the thermal battery is prepared by mixing the constituent materials of the intermediate layer uniformly and then performing any one of a tabletting stacking method and a coating stacking method.
10. Use of an interlayer of a thermal battery as claimed in claims 1 to 9 in the manufacture of a thermal battery.
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| CN104620416A (en) * | 2012-08-17 | 2015-05-13 | 得克萨斯州大学***董事会 | Porous carbon interlayer for lithium-sulfur battery |
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| CN111900351A (en) * | 2020-07-15 | 2020-11-06 | 中航锂电技术研究院有限公司 | Composite carbon material for lithium-sulfur battery, preparation method and lithium-sulfur battery |
| CN113270578A (en) * | 2021-05-17 | 2021-08-17 | 贵州梅岭电源有限公司 | High specific energy composite electrode plate for thermal battery and preparation method thereof |
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| CN104620416A (en) * | 2012-08-17 | 2015-05-13 | 得克萨斯州大学***董事会 | Porous carbon interlayer for lithium-sulfur battery |
| CN105140447A (en) * | 2015-07-23 | 2015-12-09 | 中国科学院上海硅酸盐研究所 | Functional composite membrane for lithium-sulfur battery and preparation method of functional composite membrane |
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