CN108172757A - A kind of high pressure Thermal Cell Cathode Material, high pressure thermal cell and preparation method thereof - Google Patents

A kind of high pressure Thermal Cell Cathode Material, high pressure thermal cell and preparation method thereof Download PDF

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CN108172757A
CN108172757A CN201810071718.8A CN201810071718A CN108172757A CN 108172757 A CN108172757 A CN 108172757A CN 201810071718 A CN201810071718 A CN 201810071718A CN 108172757 A CN108172757 A CN 108172757A
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lithium
high pressure
thermal cell
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ionic conductor
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CN108172757B (en
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杨潇薇
王超
冯秀丽
兰伟
刘效疆
崔益秀
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Institute of Electronic Engineering of CAEP
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    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/06—Electrodes for primary cells
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386—Silicon or alloys based on silicon
    • 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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    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/40—Alloys based on alkali metals
    • H01M4/405—Alloys based on lithium
    • 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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    • H01M4/02—Electrodes composed of, or comprising, active material
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    • H01M6/00—Primary cells; Manufacture thereof
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Abstract

The present invention discloses a kind of high pressure Thermal Cell Cathode Material and high pressure thermal cell.The thermal cell is made of positive electrode, negative material and electrolyte membrane materials, positive electrode is manganese bioxide material, Li-Si alloy material of the negative material for lithium fast-ionic conductor lithium borate-lithium sulfate cladding, electrolyte membrane materials are lithium nitrate-potassium nitrate-magnesium oxide material.The present invention coats Li-Si alloy by lithium fast-ionic conductor lithium borate-lithium sulfate, change transmission process of the metal cation in interface in the interface composition and cell operations of cathode Li-Si alloy and electrolyte lithium nitrate-potassium nitrate, diffusion rate and ionic conductivity of the lithium ion in interface passivation film layer are greatly increased, and then improves the operating voltage of thermal cell.

Description

A kind of high pressure Thermal Cell Cathode Material, high pressure thermal cell and preparation method thereof
Technical field
The present invention relates to thermal cell technical fields, and in particular to a kind of high pressure Thermal Cell Cathode Material and preparation method thereof with And the high pressure thermal cell using the high pressure Thermal Cell Cathode Material.
Background technology
Thermal cell be using disposable reserve cell of the high-temperature fusion salt as electrolyte, generally by positive plate, negative plate, Electrolyte membrance piece, heating system and activation system composition；Its operation principle is heated to be lighted Kindling paper using activation system System heats electrolyte under the action of Kindling paper makes its melting enter working condition in ion conductor；Since thermal cell has It is higher than energy, specific power is high, activation is rapid, storage time is long and for a long time it is non-maintaining the characteristics of, in military field and high-new skill Art weapon field is widely used.
At present, most thermal cells use lithium alloy/FeS2、CoS2Electrochemical system, but both of the above single battery Operating voltage is in 2V hereinafter, high-power output can be very limited；With the demand that weapon system updates, to thermoelectricity Pond power output requirement is higher and higher, and therefore, exploitation high voltage system thermal cell has broad application prospects and realistic meaning.
Invention content
In order to solve the problems in the existing technology, the object of the present invention is to provide a kind of high pressure Thermal Cell Cathode Materials And the high pressure thermal cell using the Thermal Cell Cathode Material, to solve the problems, such as that existing thermal cell operating voltage is low.
The technical solution that the present invention solves above-mentioned technical problem is as follows：A kind of high pressure Thermal Cell Cathode Material is provided, including： It is made of Li-Si alloy and the lithium fast-ionic conductor lithium borate-lithium sulfate for being coated on the Li-Si alloy surface；The lithium soon from The addition of sub- conductor lithium borate-lithium sulfate is the 10-30% of Li-Si alloy weight.
Using having the beneficial effect that for above-mentioned technical proposal：By lithium fast-ionic conductor lithium borate-lithium sulfate to Li-Si alloy It is coated, changes gold in the interface composition and cell operations of cathode Li-Si alloy and electrolyte lithium nitrate-potassium nitrate Belong to transmission process of the cation in interface, greatly increase diffusion rate and ionic conductance of the lithium ion in interface passivation film layer Rate, and then improve the operating voltage of thermal cell.
Based on the above technical solution, the present invention can also be improved as follows：
Further, the addition of the lithium fast-ionic conductor lithium borate-lithium sulfate is the 20% of Li-Si alloy weight.
Further, the lithium fast-ionic conductor lithium borate-lithium sulfate is mixed by lithium tetraborate crystal and anhydrous slufuric acid crystalline lithium It is prepared, the mass percent 30-40% of the lithium tetraborate crystal；The mass percent of anhydrous slufuric acid crystalline lithium is 60- 70%.
Further, the preparation method of the lithium fast-ionic conductor lithium borate-lithium sulfate is：
(1) lithium hydroxide and boric acid are placed in alumina crucible, constant temperature is handled 1 hour at 500 DEG C, then in air gas In atmosphere, at 600 DEG C, high temperature sintering 2 hours obtains lithium tetraborate crystal；The weight ratio of the lithium hydroxide and boric acid is 1：1；
(2) again by lithium sulfate in argon gas atmosphere, high temperature sintering 2 hours at 300 DEG C obtain anhydrous slufuric acid crystalline lithium；
(3) lithium tetraborate crystal and anhydrous slufuric acid crystalline lithium are placed in ZrO2In ball grinder, under the conditions of 370rpm, ball milling 50 Hour, lithium fast-ionic conductor lithium borate-lithium sulfate is made.
Another technical solution is as follows used by the present invention solves above-mentioned technical problem：A kind of high pressure thermoelectricity is provided Pond is made of positive electrode, negative material and electrolyte membrane materials, and by weight, the content of positive electrode is 30-50%； The content of negative material is 10-30%；The content of electrolyte membrane materials is 20-40%；Wherein, positive electrode is titanium dioxide Manganese material, negative material are claim 1-4 any one of them high pressure Thermal Cell Cathode Materials, and electrolyte membrane materials are Lithium nitrate-potassium nitrate-magnesium oxide material.
Using having the beneficial effect that for above-mentioned technical proposal：Using modified negative material and with modified negative material The specific positive electrode and electrolyte membrane materials of effect are matched, is on the one hand reduced between electrode material and electrolyte solution Side reaction reduces discharge process polarization；On the other hand, lithium ion can be greatly increased to transmit from electrolyte solution to electrode When diffusion admittance, under above-mentioned double action, considerably increase in system thermal cell of the present invention lithium ion in interface passivation film Diffusion rate and ionic conductivity in layer, and then improve the operating voltage of thermal cell.
Based on the above technical solution, the present invention can also be improved as follows：
Further, high pressure thermal cell is made of positive electrode, negative material and electrolyte membrane materials, by weight, just The content of pole material is 44%；The content of negative material is 21%；The content of electrolyte membrane materials is 35%；Wherein, anode Material is manganese bioxide material, and negative material is claim 1-4 any one of them high pressure Thermal Cell Cathode Materials, is electrolysed Matter diaphragm material is lithium nitrate-potassium nitrate-magnesium oxide material.
Another technical solution is as follows used by the present invention solves above-mentioned technical problem：Above-mentioned high pressure thermal cell is provided Preparation method, including：
By positive electrode, negative material and electrolyte membrane materials by the form of compound mold technique be pressed into high pressure lithium from Sub- thermal cell.
Based on the above technical solution, the present invention can also be improved as follows：
Further, sulfuric acid monohydrate manganese solution with liquor potassic permanganate is mixed, is reacted 2 hours at 140 DEG C, natural cooling To room temperature, obtained product is washed again with deionized water and absolute ethyl alcohol, 10-12 hours dry at 80 DEG C, obtains dioxy Change manganese material；The weight ratio of manganese sulfate monohydrate and potassium permanganate is 1:2.
Further, the preparation method of the negative material is：
Lithium fast-ionic conductor lithium borate-lithium sulfate is coated on Li-Si alloy, obtains surface cladding lithium fast-ionic conductor The Li-Si alloy negative material of lithium borate-lithium sulfate；
The preparation method of the lithium fast-ionic conductor lithium borate-lithium sulfate is：
(1) lithium hydroxide and boric acid are placed in alumina crucible, constant temperature is handled 1 hour at 500 DEG C, then in air gas In atmosphere, at 600 DEG C, high temperature sintering 2 hours obtains lithium tetraborate crystal；The weight ratio of lithium hydroxide and boric acid is 1:1；
(2) again by lithium sulfate in argon gas atmosphere, high temperature sintering 2 hours at 300 DEG C obtain anhydrous slufuric acid crystalline lithium；
(3) lithium tetraborate crystal and anhydrous slufuric acid crystalline lithium are placed in ZrO2In ball grinder, under the conditions of 370rpm, ball milling 50 Hour, lithium fast-ionic conductor lithium borate-lithium sulfate is made.
Further, the preparation method of the electrolyte membrane materials is：
Lithium nitrate and potassium nitrate are dissolved in distilled water respectively, dissolve and are uniformly dispersed, adds mass fraction as 30- 40% magnesia is heated, is stirred, dry, then be placed in inert atmosphere tube furnace, 4 are melted at 400 DEG C as flow inhibitor Hour, obtain electrolyte membrane materials；Wherein, lithium nitrate and potassium nitrate weight ratio are 1:2.
The invention has the advantages that：
The present invention changes cathode Li-Si alloy and electrolyte interface composition and electricity due to using novel negative material Transmission process of the metal cation in interface in the course of work of pond, the negative material and specific mutual cooperation therewith act on into And the positive electrode of its operating voltage and the combined composition hot high pressure battery system of electrolyte membrane materials are greatly increased, so as to increase Diffusion admittance and ionic conductivity of the lithium ion in cathode/electrolyte interface passivating film are added so that single battery electric discharge electricity Pressure is further enhanced, and specific discharge capacity is further promoted, so meet thermal cell low temperature, high voltage operation spy Point has huge application prospect.
Description of the drawings
Fig. 1 be the high pressure thermal cell that is prepared of the embodiment of the present invention 1 at 250 DEG C, with 20mA/cm2Constant current density During electric discharge, negative material before modified after, the discharge curve that measures.
Specific embodiment
The principle and features of the present invention will be described below with reference to the accompanying drawings, and the given examples are served only to explain the present invention, and It is non-to be used to limit the scope of the present invention.
Embodiment 1：
A kind of high pressure Thermal Cell Cathode Material is led by Li-Si alloy and the fast ion of lithium for being coated on the Li-Si alloy surface Body lithium borate-lithium sulfate composition；The addition of lithium fast-ionic conductor lithium borate-lithium sulfate is the 20% of Li-Si alloy weight； Lithium fast-ionic conductor lithium borate-lithium sulfate is mixed with by crystalline lithium in lithium tetraborate crystal and anhydrous slufuric acid, and lithium borate is brilliant The mass percent of body is 40%；The mass percent of anhydrous slufuric acid crystalline lithium is 60%.
The preparation method of above-mentioned lithium fast-ionic conductor lithium borate-lithium sulfate is：
1) by the LiOHH of the pure grade of starting material assay2O and H3BO3Respectively in Al2O31h is handled through 500 DEG C of constant temperature in crucible, Then the two in air atmosphere is carried out to 600 DEG C, the high temperature sintering of 2h, obtain Li3BO3Crystal；LiOH·H2O and H3BO3's Weight ratio is 1:1；
2) by the Li of the pure grade of starting material assay2SO4·H2O carries out 300 DEG C, the high temperature sintering of 2h in argon gas atmosphere, obtains Anhydrous Li2SO4Crystal；
3) finally by Li3BO3Crystal and anhydrous Li2SO4Crystal carries out mechanical ball mill and is mixed with lithium fast-ionic conductor Li3BO3- Li2SO4, specially：By Li3BO3Crystal and anhydrous Li2SO4Mixed crystal is put into ZrO2In ball grinder, setting turns Prepared by the ball milling of fast 370rpm, ball milling 50h, all mechanical milling processes and experimental implementation process are carried out in argon gas atmosphere.
Embodiment 2：
A kind of high pressure thermal cell, is made of positive electrode, negative material and electrolyte membrane materials, by weight, anode The content of material is 44%；The content of negative material is 21%；The content of electrolyte membrane materials is 35%；Wherein, anode material Expect for manganese bioxide material, negative material is by Li-Si alloy and the lithium fast-ionic conductor boric acid for being coated on Li-Si alloy surface The high pressure Thermal Cell Cathode Material of lithium-lithium sulfate composition, electrolyte membrane materials are lithium nitrate-potassium nitrate-magnesia material Material.
The preparation method of above-mentioned high pressure thermal cell is：
(1) positive electrode MnO2It prepares
Take the MnSO of 1.5mmol4·H2O is dissolved in deionized water, then takes the KMnO of 3mmol4It is dissolved in deionized water, most Afterwards, by KMnO4The reaction kettle of 50mL is transferred in solution system before solution addition, it is natural after reacting 2h at a temperature of 140 DEG C It is cooled to room temperature, obtained product uses deionized water and washes of absolute alcohol for several times respectively, is positioned over 80 DEG C of vacuum drying chamber In obtain black product MnO after dry 12 hours2Material；
(2) prepared by negative material
Lithium fast-ionic conductor Li3BO3- Li2SO4Mechanical mixture is carried out with negative material Li-Si alloy, to ensure mixing packet It covers uniformly, two kinds of materials is packed into ball grinder in an inert atmosphere, in the case where not being put into abrading-ball, on planetary ball mill Its mixing is evenly coated, it is final that surface coats Li3BO3- Li2SO4Li-Si alloy negative material；Lithium fast-ionic conductor boron The addition of sour lithium-lithium sulfate is the 20% of Li-Si alloy weight；Wherein, lithium fast-ionic conductor Li3BO3- Li2SO4Preparation Method is：
By the LiOHH of the pure grade of starting material assay2O and H3BO3Respectively in Al2O31h is handled through 500 DEG C of constant temperature in crucible, so The two in air atmosphere is carried out to 600 DEG C, the high temperature sintering of 2h afterwards, obtains Li3BO3Crystal；LiOH·H2O and H3BO3Weight Amount is than being 1:1；
By the Li of the pure grade of starting material assay2SO4·H2O carries out 300 DEG C, the high temperature sintering of 2h in argon gas atmosphere, obtains nothing Water Li2SO4Crystal；Finally by Li3BO3Crystal and anhydrous Li2SO4Crystal carries out mechanical ball mill and is mixed with lithium fast-ionic conductor Li3BO3- Li2SO4, specially：Mixture is put into ZrO2In ball grinder, rotating speed 370rpm, the ball milling system of ball milling 50h are set Standby, all mechanical milling processes and experimental implementation process are carried out in argon gas atmosphere；Li3BO3Crystal and anhydrous Li2SO4Crystal Weight ratio is 2:3.
(3) electrolyte membrane materials are prepared
Pure LiNO will be analyzed3、KNO3, being dried in vacuo at 180 DEG C makes raw material be dehydrated completely, grinds in dry environments Afterwards, it is dissolved in distilled water, each component is promoted to dissolve and be uniformly dispersed using modes such as stirring, heating, ultrasonic vibrations, add matter The MgO that amount score is 35% makees flow inhibitor, continues to heat, stir, and baking oven is transferred to after most of moisture evaporation, until institute There is moisture evaporating completely to fall, place into inert atmosphere tube furnace, after melting 4h at 400 DEG C, attrition grinding obtains finally LiNO3- KNO3MgO material, wherein, LiNO3And KNO3Weight ratio be 1:2；
(4) prepared by high pressure thermal cell
Above-mentioned positive electrode, negative material and electrolyte membrane materials are mixed using three-in-one pressed powder technique and are suppressed Into single battery, i.e. high pressure thermal cell.
Embodiment 3
A kind of high pressure Thermal Cell Cathode Material is led by Li-Si alloy and the fast ion of lithium for being coated on the Li-Si alloy surface Body lithium borate-lithium sulfate composition；The addition of lithium fast-ionic conductor lithium borate-lithium sulfate is the 10% of Li-Si alloy weight； Lithium fast-ionic conductor lithium borate-lithium sulfate is mixed with by crystalline lithium in lithium tetraborate crystal and anhydrous slufuric acid, and lithium borate is brilliant The mass percent of body is 30%；The mass percent of anhydrous slufuric acid crystalline lithium is 70%.
The preparation method of above-mentioned lithium fast-ionic conductor lithium borate-lithium sulfate is：
1) by the LiOHH of the pure grade of starting material assay2O and H3BO3Respectively in Al2O31h is handled through 500 DEG C of constant temperature in crucible, Then the two in air atmosphere is carried out to 600 DEG C, the high temperature sintering of 2h, obtain Li3BO3Crystal；LiOH·H2O and H3BO3's Weight ratio is 1:1；
2) by the Li of the pure grade of starting material assay2SO4·H2O carries out 300 DEG C, the high temperature sintering of 2h in argon gas atmosphere, obtains Anhydrous Li2SO4Crystal；
3) finally by Li3BO3Crystal and anhydrous Li2SO4Crystal carries out mechanical ball mill and is mixed with lithium fast-ionic conductor Li3BO3- Li2SO4, specially：By Li3BO3Crystal and anhydrous Li2SO4Mixed crystal is put into ZrO2In ball grinder, setting turns Fast 370rpm, ball milling 50h, all mechanical milling processes and experimental implementation process are carried out in argon gas atmosphere.
Embodiment 4
A kind of high pressure thermal cell, is made of positive electrode, negative material and electrolyte membrane materials, by weight, anode The content of material is 35%；The content of negative material is 28%；The content of electrolyte membrane materials is 37%；Wherein, anode material Expect for manganese bioxide material, negative material is by Li-Si alloy and the lithium fast-ionic conductor boric acid for being coated on Li-Si alloy surface The high pressure Thermal Cell Cathode Material of lithium-lithium sulfate composition, electrolyte membrane materials are lithium nitrate-potassium nitrate-magnesia material Material.
The preparation method of above-mentioned high pressure thermal cell is：
(1) positive electrode MnO2It prepares
Take the MnSO of 1.5mmol4·H2O is dissolved in deionized water, then takes the KMnO of 3mmol4It is dissolved in deionized water, most Afterwards, by KMnO4The reaction kettle of 50mL is transferred in solution system before solution addition, it is natural after reacting 2h at a temperature of 140 DEG C It is cooled to room temperature, obtained product uses deionized water and washes of absolute alcohol for several times respectively, is positioned over 80 DEG C of vacuum drying chamber In obtain black product MnO after dry 12 hours2Material；
(2) prepared by negative material
Lithium fast-ionic conductor Li3BO3- Li2SO4Mechanical mixture is carried out with negative material Li-Si alloy, to ensure mixing packet It covers uniformly, two kinds of materials is packed into ball grinder in an inert atmosphere, in the case where not being put into abrading-ball, on planetary ball mill Its mixing is evenly coated, it is final that surface coats Li3BO3- Li2SO4Li-Si alloy negative material；Lithium fast-ionic conductor boron The addition of sour lithium-lithium sulfate is the 10% of Li-Si alloy weight；Wherein, lithium fast-ionic conductor Li3BO3- Li2SO4Preparation Method is：
By the LiOHH of the pure grade of starting material assay2O and H3BO3Respectively in Al2O31h is handled through 500 DEG C of constant temperature in crucible, so The two in air atmosphere is carried out to 600 DEG C, the high temperature sintering of 2h afterwards, obtains Li3BO3Crystal；LiOH·H2O and H3BO3Weight Amount is than being 1:1；
By the Li of the pure grade of starting material assay2SO4·H2O carries out 300 DEG C, the high temperature sintering of 2h in argon gas atmosphere, obtains nothing Water Li2SO4Crystal；Finally by Li3BO3Crystal and anhydrous Li2SO4Crystal carries out mechanical ball mill and is mixed with lithium fast-ionic conductor Li3BO3- Li2SO4, specially：Mixture is put into ZrO2In ball grinder, rotating speed 370rpm, the ball milling system of ball milling 50h are set Standby, all mechanical milling processes and experimental implementation process are carried out in argon gas atmosphere；Li3BO3Crystal and anhydrous Li2SO4Crystal Weight ratio is 3：7.
(3) electrolyte membrane materials are prepared
Pure LiNO will be analyzed3、KNO3, being dried in vacuo at 180 DEG C makes raw material be dehydrated completely, grinds in dry environments Afterwards, it is dissolved in distilled water, each component is promoted to dissolve and be uniformly dispersed using modes such as stirring, heating, ultrasonic vibrations, add matter The MgO that amount score is 40% makees flow inhibitor, continues to heat, stir, and baking oven is transferred to after most of moisture evaporation, until institute There is moisture evaporating completely to fall, place into inert atmosphere tube furnace, after melting 4h at 400 DEG C, attrition grinding obtains finally LiNO3- KNO3- MgO electrolyte membrane materials, wherein, LiNO3And KNO3Weight ratio be 1:2；
(4) prepared by high pressure thermal cell
Above-mentioned positive electrode, negative material and electrolyte membrane materials are mixed using three-in-one pressed powder technique and are suppressed Into single battery, i.e. high pressure thermal cell.
Embodiment 5
A kind of high pressure Thermal Cell Cathode Material is led by Li-Si alloy and the fast ion of lithium for being coated on the Li-Si alloy surface Body lithium borate-lithium sulfate composition；The addition of lithium fast-ionic conductor lithium borate-lithium sulfate is the 30% of Li-Si alloy weight； Lithium fast-ionic conductor lithium borate-lithium sulfate is mixed with by crystalline lithium in lithium tetraborate crystal and anhydrous slufuric acid, and lithium borate is brilliant The mass percent of body is 35%；The mass percent of anhydrous slufuric acid crystalline lithium is 65%.
The preparation method of above-mentioned lithium fast-ionic conductor lithium borate-lithium sulfate is：
1) by the LiOHH of the pure grade of starting material assay2O and H3BO3Respectively in Al2O31h is handled through 500 DEG C of constant temperature in crucible, Then the two in air atmosphere is carried out to 600 DEG C, the high temperature sintering of 2h, obtain Li3BO3Crystal；LiOH·H2O and H3BO3's Weight ratio is 1:1；
2) by the Li of the pure grade of starting material assay2SO4·H2O carries out 300 DEG C, the high temperature sintering of 2h in argon gas atmosphere, obtains Anhydrous Li2SO4Crystal；
3) finally by Li3BO3Crystal and anhydrous Li2SO4Crystal carries out mechanical ball mill and is mixed with lithium fast-ionic conductor Li3BO3- Li2SO4, specially：By Li3BO3Crystal and anhydrous Li2SO4Mixed crystal is put into ZrO2In ball grinder, setting turns Fast 370rpm, ball milling 50h, all mechanical milling processes and experimental implementation process are carried out in argon gas atmosphere.
Embodiment 6
A kind of high pressure thermal cell, is made of positive electrode, negative material and electrolyte membrane materials, by weight, anode The content of material is 40%；The content of negative material is 20%；The content of electrolyte membrane materials is 40%；Wherein, anode material Expect for manganese bioxide material, negative material is by Li-Si alloy and the lithium fast-ionic conductor boric acid for being coated on Li-Si alloy surface The high pressure Thermal Cell Cathode Material of lithium-lithium sulfate composition, electrolyte membrane materials are lithium nitrate-potassium nitrate-magnesia material Material.
The preparation method of above-mentioned high pressure thermal cell is：
(1) positive electrode MnO2It prepares
Take the MnSO of 1.5mmol4·H2O is dissolved in deionized water, then takes the KMnO of 3mmol4It is dissolved in deionized water, most Afterwards, by KMnO4The reaction kettle of 50mL is transferred in solution system before solution addition, it is natural after reacting 2h at a temperature of 140 DEG C It is cooled to room temperature, obtained product uses deionized water and washes of absolute alcohol for several times respectively, is positioned over 80 DEG C of vacuum drying chamber In obtain black product MnO after dry 12 hours2Material；
(2) prepared by negative material
Lithium fast-ionic conductor Li3BO3- Li2SO4Mechanical mixture is carried out with negative material Li-Si alloy, to ensure mixing packet It covers uniformly, two kinds of materials is packed into ball grinder in an inert atmosphere, in the case where not being put into abrading-ball, on planetary ball mill Its mixing is evenly coated, it is final that surface coats Li3BO3- Li2SO4Li-Si alloy negative material；Lithium fast-ionic conductor boron The addition of sour lithium-lithium sulfate is the 30% of Li-Si alloy weight；Wherein, lithium fast-ionic conductor Li3BO3- Li2SO4Preparation Method is：
By the LiOHH of the pure grade of starting material assay2O and H3BO3Respectively in Al2O31h is handled through 500 DEG C of constant temperature in crucible, so The two in air atmosphere is carried out to 600 DEG C, the high temperature sintering of 2h afterwards, obtains Li3BO3Crystal；LiOH·H2O and H3BO3Weight Amount is than being 1:1；
By the Li of the pure grade of starting material assay2SO4·H2O carries out 300 DEG C, the high temperature sintering of 2h in argon gas atmosphere, obtains nothing Water Li2SO4Crystal；Finally by Li3BO3Crystal and anhydrous Li2SO4Crystal carries out mechanical ball mill and is mixed with lithium fast-ionic conductor Li3BO3- Li2SO4, specially：Mixture is put into ZrO2In ball grinder, rotating speed 370rpm, ball milling 50h, all ball millings are set Process and experimental implementation process are carried out in argon gas atmosphere；Li3BO3Crystal and anhydrous Li2SO4The weight ratio of crystal is 7： 13。
(3) electrolyte membrane materials are prepared
Pure LiNO will be analyzed3、KNO3, being dried in vacuo at 180 DEG C makes raw material be dehydrated completely, grinds in dry environments Afterwards, it is dissolved in distilled water, each component is promoted to dissolve and be uniformly dispersed using modes such as stirring, heating, ultrasonic vibrations, add matter The MgO that amount score is 40% makees flow inhibitor, continues to heat, stir, and baking oven is transferred to after most of moisture evaporation, until institute There is moisture evaporating completely to fall, place into inert atmosphere tube furnace, after melting 4h at 400 DEG C, attrition grinding obtains finally LiNO3- KNO3- MgO electrolyte membrane materials, wherein, LiNO3And KNO3Weight ratio be 1:2；
(4) prepared by high pressure thermal cell
Above-mentioned positive electrode, negative material and electrolyte membrane materials are mixed using three-in-one pressed powder technique and are suppressed Into single battery, i.e. high pressure thermal cell.
Test example
The performance of high pressure thermal cell that embodiment 2 is prepared is tested
Fig. 1 is that high pressure thermal cell prepared by the embodiment of the present invention 2 in operating temperature is 250 DEG C, current density 20mA/ cm2When discharge curve, the monomer high pressure thermal cell initial discharge voltage after interface modification is 3.168V, voltage in discharge process Decline is slower, and specific discharge capacity is 886.5mAh/g when 2.0V, and specific discharge capacity is when 0.1V 2072.4mAh/g；
And the single battery initial discharge voltage of interface modification is not carried out as 3.166V, specific discharge capacity when 2.0V For 474.2mAh/g, specific discharge capacity is 1639.2mAh/g when 0.1V；After interface modification, switch-board thermoelectric pond is entire In discharge process, discharge voltage and specific discharge capacity all significantly improve.
The foregoing is merely presently preferred embodiments of the present invention, is not intended to limit the invention, it is all the present invention spirit and Within principle, any modification, equivalent replacement, improvement and so on should all be included in the protection scope of the present invention.

Claims (10)

1. high pressure Thermal Cell Cathode Material, which is characterized in that fast by Li-Si alloy and the lithium for being coated on the Li-Si alloy surface Ion conductor lithium borate-lithium sulfate composition；The addition of the lithium fast-ionic conductor lithium borate-lithium sulfate is Li-Si alloy weight The 10-30% of amount.
2. high pressure Thermal Cell Cathode Material according to claim 1, which is characterized in that the lithium fast-ionic conductor boric acid The addition of lithium-lithium sulfate is the 20% of Li-Si alloy weight.
3. high pressure Thermal Cell Cathode Material according to claim 1, which is characterized in that the lithium fast-ionic conductor boric acid Lithium-lithium sulfate is mixed with by lithium tetraborate crystal and anhydrous slufuric acid crystalline lithium, the mass percent of the lithium tetraborate crystal For 30-40%；The mass percent of anhydrous slufuric acid crystalline lithium is 60-70%.
4. high pressure Thermal Cell Cathode Material according to claim 3, which is characterized in that lithium fast-ionic conductor lithium borate-sulphur The preparation method of sour lithium is：
(1) lithium hydroxide and boric acid are placed in alumina crucible, constant temperature is handled 1 hour at 500 DEG C, then in air atmosphere In, at 600 DEG C, high temperature sintering 2 hours obtains lithium tetraborate crystal；The weight ratio of the lithium hydroxide and boric acid is 1：1；
(2) again by lithium sulfate in argon gas atmosphere, high temperature sintering 2 hours at 300 DEG C obtain anhydrous slufuric acid crystalline lithium；
(3) lithium tetraborate crystal and anhydrous slufuric acid crystalline lithium are placed in ZrO2In ball grinder, under the conditions of 370rpm, ball milling 50 hours, Lithium fast-ionic conductor lithium borate-lithium sulfate is made.
5. a kind of high pressure thermal cell, which is characterized in that be made of positive electrode, negative material and electrolyte membrane materials, with weight Gauge, the content of positive electrode is 30-50%；The content of negative material is 10-30%；The content of electrolyte membrane materials is 20-40%；Wherein, positive electrode is manganese bioxide material, and negative material is claim 1-4 any one of them hot high pressures Cell negative electrode material, electrolyte membrane materials are lithium nitrate-potassium nitrate-magnesium oxide material.
6. high pressure thermal cell according to claim 5, which is characterized in that by positive electrode, negative material and electrolyte every Membrane material forms, and by weight, the content of positive electrode is 44%；The content of negative material is 21%；Electrolyte membrane materials Content be 35%；Wherein, positive electrode is manganese bioxide material, and negative material is high for claim 1-4 any one of them Thermal Cell Cathode Material is pressed, electrolyte membrane materials are lithium nitrate-potassium nitrate-magnesium oxide material.
7. the preparation method of high pressure thermal cell described in claim 5 or 6, which is characterized in that including：
Positive electrode, negative material and electrolyte membrane materials are pressed into high pressure lithium ion heat by the form of compound mold technique Battery.
8. the preparation method of high pressure thermal cell according to claim 7, which is characterized in that the preparation side of the positive electrode Method is：
Sulfuric acid monohydrate manganese solution with liquor potassic permanganate is mixed, is reacted 2 hours at 140 DEG C, cooled to room temperature obtains Product washed again with deionized water and absolute ethyl alcohol, be dried in vacuo 10-12 hours at 80 DEG C, obtain manganese dioxide material Material；The weight ratio of manganese sulfate monohydrate and potassium permanganate is 1:2.
9. the preparation method of high pressure lithium ion thermal cell according to claim 7, which is characterized in that the negative material Preparation method is：
Lithium fast-ionic conductor lithium borate-lithium sulfate is coated on Li-Si alloy, obtains surface cladding lithium fast-ionic conductor boric acid The Li-Si alloy negative material of lithium-lithium sulfate；
The preparation method of the lithium fast-ionic conductor lithium borate-lithium sulfate is：
(1) lithium hydroxide and boric acid being placed in alumina crucible, constant temperature handles 1h at 500 DEG C, then in air atmosphere, At 600 DEG C, high temperature sintering 2 hours obtains lithium tetraborate crystal；The weight ratio of lithium hydroxide and boric acid is 1:1；
(2) again by lithium sulfate in argon gas atmosphere, high temperature sintering 2 hours at 300 DEG C obtain anhydrous slufuric acid crystalline lithium；
(3) lithium tetraborate crystal and anhydrous slufuric acid crystalline lithium are placed in ZrO2In ball grinder, under the conditions of 370rpm, ball milling 50 hours, Lithium fast-ionic conductor lithium borate-lithium sulfate is made.
10. the preparation method of high pressure lithium ion thermal cell according to claim 7, which is characterized in that the electrolyte every The preparation method of membrane material is：
Lithium nitrate and potassium nitrate are dissolved in distilled water respectively, dissolve and are uniformly dispersed, adds mass fraction as 30-40% Magnesia as flow inhibitor, heat, stir, it is small to melt 4 for drying, then be placed in inert atmosphere tube furnace at 400 DEG C When, obtain electrolyte membrane materials；Wherein, lithium nitrate and potassium nitrate weight ratio are 1:2.
CN201810071718.8A 2018-01-24 2018-01-24 High-voltage thermal battery negative electrode material, high-voltage thermal battery and preparation method of high-voltage thermal battery negative electrode material Expired - Fee Related CN108172757B (en)

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