CN112670528B - Preparation method of high-rate primary alkali metal battery - Google Patents
Preparation method of high-rate primary alkali metal battery Download PDFInfo
- Publication number
- CN112670528B CN112670528B CN202011555032.XA CN202011555032A CN112670528B CN 112670528 B CN112670528 B CN 112670528B CN 202011555032 A CN202011555032 A CN 202011555032A CN 112670528 B CN112670528 B CN 112670528B
- Authority
- CN
- China
- Prior art keywords
- battery
- graphite
- sheets
- graphite fluoride
- metal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The embodiment of the invention provides a preparation method of a high-rate primary alkali metal battery, which comprises the steps of shearing, emulsifying and homogenizing worm graphite to obtain graphite micro-sheets, carrying out high-temperature fluorination with the assistance of alloy balls to obtain graphite fluoride micro-sheets, dissolving the graphite fluoride micro-sheets serving as active substances, a conductive agent and a binder in proportion, pulping, coating the active substances on a current collector, drying and cutting to obtain a battery anode; wherein, the proportion of C=C bonds on the surface of the graphite fluoride micron sheet is 5-15%; removing a surface passivation layer from the metal sodium block or the metal potassium block, dropwise adding a plurality of electrolyte, and calendaring and cutting the metal sodium block or the metal potassium block into metal sodium sheets or metal potassium sheets with a first size through mechanical action to serve as a battery cathode; assembling a battery anode, a battery cathode, a diaphragm and electrolyte to obtain a sodium/graphite fluoride micron-sized primary battery or a potassium/graphite fluoride micron-sized primary battery; the battery has excellent discharge rate performance, wide working temperature range, good storage performance, excellent comprehensive performance and large application potential.
Description
Technical Field
The invention relates to the field of primary batteries, in particular to a preparation method of a high-rate primary alkali metal battery.
Background
With the continuous development of new energy scenes, lithium Ion Batteries (LIB) are widely applied, but in special application scenes such as aerospace, medical treatment and the like, lithium primary batteries can generally provide higher energy density, longer shelf life and wider working temperature range, which cannot be provided by the current lithium ion batteries.
The lithium/carbon fluoride battery is a lithium primary battery taking metal lithium as a negative electrode and taking a carbon fluoride material as a positive electrode, has the characteristics of high specific energy, stable discharge performance, long storage life, no toxicity, no pollution and the like, is a primary battery system with the best performance at present, and is widely applied to a plurality of fields such as military, aerospace, medical treatment, civilian use and the like.
The lithium resources on the earth are unevenly distributed, and the problems of difficult exploitation, rising price and the like exist, so that the development of the lithium battery taking lithium salt or lithium metal as an electrode is greatly restricted. In order to meet future energy storage demands, alternatives to lithium are being sought among other alkali metals. At present, due to the advantages of wide sources of sodium and potassium, low cost and the like, a battery system using sodium or potassium as an electrode is correspondingly developed, but compared with lithium ions, the radius of the sodium and potassium ions is larger, the intercalation/deintercalation resistance in the anode and the cathode is larger, so that the reversibility of the sodium and potassium batteries is poor, the irreversible capacity loss is large, and the cycle performance is poor.
Disclosure of Invention
In view of the above, the invention provides a preparation method of a high-rate primary alkali metal battery, and a sodium/graphite fluoride micro-sheet and potassium/graphite fluoride micro-sheet primary battery with high discharge rate and high specific capacity is obtained.
In order to achieve the above purpose, the technical scheme of the invention is realized as follows:
the embodiment of the invention provides a preparation method of a high-rate primary alkali metal battery, which comprises the following steps:
shearing, emulsifying and homogenizing worm graphite to obtain graphite micro-sheets, carrying out high-temperature fluorination with the aid of alloy balls to obtain graphite fluoride micro-sheets, dissolving the graphite fluoride micro-sheets serving as active substances, a conductive agent and a binder in proportion, pulping, coating the active substances on a current collector, drying and cutting to obtain a battery anode; wherein the proportion of C=C bonds on the surface of the graphite fluoride micron sheet is 5-15%;
removing a surface passivation layer from the metal sodium block or the metal potassium block, dropwise adding a plurality of electrolyte, and calendaring and cutting the metal sodium block or the metal potassium block into metal sodium sheets or metal potassium sheets with a first size through mechanical action to serve as a battery cathode;
and assembling the battery anode, the battery cathode, the diaphragm and the electrolyte to obtain the sodium/graphite fluoride micron-sized sheet primary battery or the potassium/graphite fluoride micron-sized sheet primary battery.
Wherein the method further comprises:
(1) Mixing worm graphite with granularity of 10-100 micrometers in deionized water according to the proportion of 10-20%, shearing and emulsifying the mixed solution at a high speed of 2000-4000 rpm for 30-90 minutes, then maintaining the homogeneous solution for 30-60 minutes under the pressure of 1000-1500 pascals by a high-pressure homogenizer, and carrying out suction filtration and vacuum drying to obtain graphite micrometer sheets;
(2) Adding the graphite micron sheets and alloy balls with different sizes and proportions into a fluorination furnace with stirring paddles, sealing, vacuumizing, removing oxygen and moisture in a bin by using inert gas at 100 ℃, and repeating for 3 times;
(3) Turning on a stirring paddle at the rotating speed of 100-500 rpm, turning over the alloy balls and the graphite micron sheets, switching fluorine/nitrogen mixed gas with the gas of 20%, controlling the pressure to be 80-90 kilopascals, and running for 30 minutes;
(4) Controlling the temperature in the furnace, firstly heating to 180 ℃ at a heating rate of 2 ℃ per minute, preserving heat for 1-3 hours, then heating to 400-500 ℃ at a heating rate of 4 ℃ per minute, preserving heat for 3-6 hours, controlling the cooling rate to 4-6 ℃ per minute until the temperature reaches the room temperature, vacuumizing, treating residual fluorine gas and byproducts in the extracted furnace by alkali liquor, and sieving the materials in the furnace by a 5-mesh screen to obtain the graphite fluoride micro-sheet.
The alloy balls are obtained by processing Monel alloy, the diameters of the alloy balls are 5, 10 and 15 millimeters, the number ratio of the alloy balls with different diameters is 4:2:1, and the mass ratio of the alloy balls to the graphite micron sheets is 10-30:1.
Wherein saidThe fluorine-carbon ratio of the graphite fluoride micron sheet is 0.8-1.1, and the conductivity is 1 multiplied by 10 -8 To 9X 10 -8 The Siemens/meter range, the size distribution is 2-30 microns.
In the battery anode, the mass percentage of the graphite fluoride micron sheet is 80-94%, the mass percentage of the conductive agent is 3-15%, and the mass percentage of the binder is 3-10%.
In the battery anode, the conductive agent is at least one of acetylene black, ketjen black, super-P and carbon nano tubes, the adhesive is polytetrafluoroethylene or polyvinylidene fluoride, the solvent is N-methyl pyrrolidone, and the current collector is aluminum foil or carbon-coated aluminum foil.
In the battery cathode, the mass of the pre-added electrolyte is 1-3% of the mass of the metal blocks in the processing process of the sodium metal block and the potassium metal block.
Wherein, the battery can discharge at a low temperature of between-30 and 0 ℃ and at a high temperature of between 40 and 100 ℃.
The invention provides a preparation method of a high-rate primary alkali metal battery, which has the beneficial effects that:
(1) On the basis of a conventional high-temperature fluorination process, the high-temperature fluorination is assisted by adding the alloy balls for grinding, so that the graphite fluoride micro-sheet with high C=C bond content on the surface is obtained, the fluorine-carbon ratio and the conductivity are high, and the graphite fluoride micro-sheet is used as an anode active material, so that high specific capacity and excellent multiplying power performance can be provided for a battery;
(2) The sodium/graphite fluoride micro-sheet primary battery and the potassium/graphite fluoride micro-sheet primary battery are novel primary battery systems, and compared with lithium, the sodium and potassium are rich in reserves and low in cost, and are expected to replace the lithium primary battery;
(3) The alkaline metal sodium and potassium primary battery has excellent electrochemical performance and high discharge multiplying power, wherein the sodium primary battery can bear 4000 milliamp/g current density discharge, the potassium primary battery can bear 3000 milliamp/g discharge, and meanwhile, the battery can discharge in a wide temperature range of-30 ℃ to 100 ℃, has good storage performance at normal temperature and has huge application potential.
Drawings
FIG. 1 is a scanning electron microscope image of a graphite fluoride microchip according to an embodiment of the present invention;
FIG. 2 is an electrogram of a sodium/graphite fluoride micro-plate primary battery provided in an embodiment of the present invention;
FIG. 3 is an electrogram of a potassium/graphite fluoride micro-plate primary battery provided in an embodiment of the present invention;
FIG. 4 is a high and low temperature discharge diagram of a sodium/graphite fluoride microchip primary cell according to an embodiment of the present invention;
FIG. 5 is a high and low temperature discharge diagram of a potassium/graphite fluoride micro-sheet primary cell according to one embodiment of the present invention;
FIG. 6 is a graph of storage performance of a sodium/graphite fluoride micro-sheet primary cell provided in an embodiment of the present invention;
fig. 7 is a graph of storage performance of a potassium/graphite fluoride micro-plate primary cell provided in an embodiment of the present invention.
Detailed Description
The present invention will be described in further detail with reference to the drawings and examples. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
Before explaining the present invention in further detail, terms and terminology involved in the embodiments of the present invention are explained, and the terms and terminology involved in the embodiments of the present invention are applicable to the following explanation.
1) Direct fluorination: the material is directly treated by fluorine-containing gas.
2) Worm graphite: vermicular graphite, also known as expanded graphite.
3) Monel alloy: the alloy is also called nickel alloy, which is an alloy formed by taking metallic nickel as a matrix and adding other elements such as copper, iron, manganese and the like, and has excellent corrosion resistance.
4) Fluorine-carbon ratio: the ratio of fluorine atoms to carbon atoms in the graphite fluoride reflects the degree of fluorination.
5) C=c bond: namely carbon-carbon double bonds, in graphite fluoride and graphene fluoride materials, the conductivity of the materials can be directly influenced by the carbon-carbon double bonds on the surfaces of the materials.
6) Rate capability: the discharge capacity of the battery is represented, and the higher the discharge current density is, the stronger the high-rate discharge capacity of the battery is.
7) Storage performance: the closer the electrochemical performance is to the initial performance after the battery has been subjected to different storage dates, the better the battery storage performance is indicated.
Referring to fig. 1-7, in order to provide a preparation method of a high-rate primary alkali metal battery according to an embodiment of the present invention, graphite micro-sheets are obtained by shearing, emulsifying and homogenizing vermicular graphite, then high-temperature fluorination is performed with the assistance of alloy balls to obtain graphite fluoride micro-sheets, the graphite fluoride micro-sheets are used as active materials, and are dissolved with a conductive agent and a binder in proportion, slurried and coated on a current collector, and then dried and cut to obtain a battery anode; wherein, the proportion of C=C bonds on the surface of the graphite fluoride micron sheet is 5-15%; removing a surface passivation layer from the metal sodium block or the metal potassium block, dropwise adding a plurality of electrolyte, and calendaring and cutting the metal sodium block or the metal potassium block into metal sodium sheets or metal potassium sheets with a first size through mechanical action to serve as a battery cathode; assembling a battery anode, a battery cathode, a diaphragm and electrolyte to obtain a sodium/graphite fluoride micron-sized primary battery or a potassium/graphite fluoride micron-sized primary battery; the battery has excellent discharge rate performance, wide working temperature range, good storage performance, excellent comprehensive performance and large application potential.
In one embodiment, the high shear emulsification and homogenization treatment comprises: mixing worm graphite in 10-20% proportion into deionized water, shearing and emulsifying the mixed solution at 2000-4000 rpm for 30-90 min, maintaining the homogeneous solution at 1000-1500 Pa for 30-60 min, suction filtering and vacuum drying to obtain the graphite micron sheet.
In an embodiment, the alloy balls are obtained by processing Monel alloy, the diameters of the alloy balls are 5, 10 and 15 mm, the number ratio of the alloy balls with different diameters is 4:2:1, the mass ratio of the alloy balls to the graphite micron sheets is 10-30:1, and the rotating stirring paddles drive the alloy balls to turn and roll the fluorinated materials together, so that the dynamic process enables the fluorination reaction to be more uniform, the fluorination goes deeper into the material, and the effect of reserving more C=C bonds on the surface of the material is achieved.
In one embodiment, the high temperature fluorination keeps the alloy ball and the stirring paddle running during the fluorination process, and meanwhile, 20% fluorine/nitrogen mixed gas is introduced as a fluorinating agent; the temperature control program of the fluorination furnace is as follows: heating to 180 ℃ at a heating rate of 2 ℃ per minute, preserving heat for 1-3 hours, heating to 400-500 ℃ at a heating rate of 4 ℃ per minute, preserving heat for 3-6 hours, and controlling a cooling rate to 4-6 ℃ per minute to cool to room temperature.
In one embodiment, the fluorine-carbon ratio of the graphite fluoride micro-sheet is 0.8-1.1, and the conductivity is 1X 10 -8 To 9X 10 -8 The Siemens/meter range, the size distribution is 2-30 microns.
In one embodiment, the battery positive electrode comprises 80-94% of graphite fluoride micron sheets, 3-15% of conductive agents and 3-10% of binders by mass; the conductive agent is at least one of acetylene black, ketjen black, super-P and carbon nano tube, the binder is polytetrafluoroethylene or polyvinylidene fluoride, the solvent is N-methyl pyrrolidone, and the current collector is aluminum foil or carbon-coated aluminum foil.
In the battery cathode, the mass of the pre-added electrolyte is 1-3% of the mass of the metal blocks in the processing process of the sodium metal block and the potassium metal block.
In one embodiment, the battery assembly, the separator is a cellgard-2500 monolayer polypropylene separator and the electrolyte is 1M NaPF 6 (EC: pc=1:1, vol.) and 1M KPF 6 (EC:PC＝1:1,vol.)。
The following describes the invention in more detail with reference to examples, which are not intended to limit the invention thereto.
Example 1
In this embodiment, the prepared graphite fluoride micro-sheet with a fluorocarbon ratio of 1.05 and a surface c=c bond ratio of 15% is used as a positive electrode, and sodium sheets and potassium sheets are used as negative electrodes to assemble a battery, which comprises the following specific steps:
(1) Mixing worm graphite with granularity of 10-100 micrometers in deionized water at a proportion of 15%, shearing and emulsifying the mixed solution at a speed of 3000 rpm for 60 minutes, then keeping the homogeneous solution under 1500 pascals pressure for 60 minutes by a high-pressure homogenizer, and carrying out suction filtration and vacuum drying to obtain a graphite micrometer sheet;
(2) Selecting Monel alloy balls with diameters of 5, 10 and 15 millimeters for assisting high-temperature fluorination, wherein the number ratio of the balls with different diameters is 4:2:1, adding the Monel alloy balls with different diameters and the graphite fluoride micro-sheets prepared in step (1) into a fluorination furnace with stirring paddles according to the mass ratio of 20:1, sealing, vacuumizing, removing oxygen and moisture in a bin at 100 ℃ by using inert gas, and repeating for 3 times;
(3) Turning on a stirring paddle, setting the rotating speed of the stirring paddle to be 300 revolutions per minute, setting the turning period to be 15 minutes, turning and stirring the mixed material of the graphite fluoride micron sheets and the Monel alloy balls in a forward and reverse alternate mode, slowly introducing 20% fluorine/nitrogen mixed gas into a sealed bin, controlling the pressure to be 90 kilopascals, and running for 30 minutes at normal temperature;
(4) The method comprises the steps of controlling the temperature in a furnace to carry out high-temperature fluorination, simultaneously keeping the rotation of a stirring paddle and a Monel alloy ball, firstly heating to 180 ℃ at a heating speed of 2 ℃ per minute, preserving heat for 1 hour, then heating to 500 ℃ at a heating speed of 4 ℃ per minute, preserving heat for 6 hours, and controlling a cooling speed of 4 ℃ per minute until the room temperature is reached;
(5) Then vacuumizing, treating residual fluorine and byproducts in the extracted furnace by alkali liquor, and separating alloy balls from the materials in the furnace by a 5-mesh screen to finally obtain the graphite fluoride micro-sheets;
(6) Dissolving the graphite fluoride micro-sheet prepared in the step (5) serving as a positive electrode active material and ketjen black and polyvinylidene fluoride in a ratio of 80:10:10 in N-methyl pyrrolidone, uniformly stirring, coating the mixture on a carbon-coated aluminum foil, drying, and cutting into a battery positive electrode sheet;
(7) Removing the passivation layer on the surface of the sodium metal block and the potassium metal block, dripping electrolyte on the surface of the metal block in advance, wherein the mass of the electrolyte is 2% of that of the metal block, and tabletting the metal block to be used as a battery cathode through mechanical action;
(8) Assembling the positive and negative plates in (6) and (7) with a celgard-2500 type diaphragm and electrolyte into a battery;
the battery in this example shows excellent rate capability, wherein the maximum discharge current density of the sodium/graphite fluoride micro-sheet battery can reach 4000 milliamp/g, the discharge specific capacity is 448.13 milliamp/g, the maximum discharge current density of the potassium/graphite fluoride micro-sheet battery can reach 3000 milliamp/g, and the discharge specific capacity is 428.44 milliamp/g, as shown in fig. 2 and 3 in detail;
example two
In this embodiment, the prepared graphite fluoride micro-sheet with a fluorocarbon ratio of 1.07 and a surface c=c bond ratio of 7% is used as a positive electrode, and sodium sheets and potassium sheets are used as negative electrodes to assemble a battery, which comprises the following specific steps:
in this example, compared with the first example, the mass ratio of the alloy balls to graphite in the step (2) was adjusted from 20:1 to 30:1, and other experimental conditions were the same as in the first example;
the maximum discharge current density of the sodium/graphite fluoride micro-sheet battery prepared in the embodiment can reach 3000 milliamp/gram, the discharge specific capacity is 488.17 milliamp/gram, the maximum discharge current density of the potassium/graphite fluoride micro-sheet battery can reach 2000 milliamp/gram, and the discharge specific capacity is 476.93 milliamp/gram.
Example III
In the embodiment, the prepared graphite fluoride micro-sheet with the fluorine-carbon ratio of 1.04 and the surface C=C bond ratio of 10% is taken as a positive electrode, and sodium sheets and potassium sheets are taken as negative electrodes to assemble the battery, and the battery is specifically as follows:
compared with the first embodiment, the mass ratio of the alloy balls to the graphite in the step (2) is reduced from 20:1 to 10:1, and other experimental conditions are the same as the first embodiment;
the maximum discharge current density of the sodium/graphite fluoride micro-sheet battery prepared in the embodiment can reach 3300 milliamp/gram, the discharge specific capacity is 465.47 milliamp/gram, the maximum discharge current density of the potassium/graphite fluoride micro-sheet battery can reach 2600 milliamp/gram, and the discharge specific capacity is 421.87 milliamp/gram.
Example IV
In this embodiment, the prepared graphite fluoride micro-sheet with a fluorocarbon ratio of 1.05 and a surface c=c bond ratio of 12% is used as a positive electrode, and sodium sheets and potassium sheets are used as negative electrodes to assemble a battery, which comprises the following specific steps:
compared with the first embodiment, the rotation speed of the stirring paddle in the step (3) is reduced from 300 rpm to 200 rpm, and other experimental conditions are the same as the first embodiment;
the maximum discharge current density of the sodium/graphite fluoride micro-sheet battery prepared in the embodiment can reach 3500 milliamp/gram, the discharge specific capacity is 468.89 milliamp/gram, the maximum discharge current density of the potassium/graphite fluoride micro-sheet battery can reach 2200 milliamp/gram, and the discharge specific capacity is 472.38 milliamp/gram.
Example five
In this embodiment, the prepared graphite fluoride micro-sheet with a fluorocarbon ratio of 1.05 and a surface c=c bond ratio of 13% is used as a positive electrode, and sodium sheets and potassium sheets are used as negative electrodes to assemble a battery, which comprises the following specific steps:
compared with the first embodiment, the rotation speed of the stirring paddle in the step (3) is increased from 300 rpm to 400 rpm, and other experimental conditions are the same as the first embodiment;
the maximum discharge current density of the sodium/graphite fluoride micro-sheet battery prepared in the embodiment can reach 3600 milliamp/gram, the discharge specific capacity is 462.32 milliamp/gram, the maximum discharge current density of the potassium/graphite fluoride micro-sheet battery can reach 2600 milliamp/gram, and the discharge specific capacity is 439.99 milliamp/gram.
Example six
In this embodiment, the prepared graphite fluoride micro-sheet with a fluorocarbon ratio of 0.89 and a surface c=c bond ratio of 6% is used as a positive electrode, and sodium sheets and potassium sheets are used as negative electrodes to assemble a battery, which comprises the following specific steps:
compared with the first embodiment, the high-temperature fluorination heat preservation temperature in the step (4) is reduced from 500 ℃ to 400 ℃, and other experimental conditions are the same as the first embodiment;
the maximum discharge current density of the sodium/graphite fluoride micro-sheet battery prepared in the embodiment can reach 2800 milliamp/gram, the discharge specific capacity is 418.49 milliamp/gram, the maximum discharge current density of the potassium/graphite fluoride micro-sheet battery can reach 1900 milliamp/gram, and the discharge specific capacity is 422.25 milliamp/gram.
Example seven
In this embodiment, the prepared graphite fluoride micro-sheet with a fluorocarbon ratio of 0.94 and a surface c=c bond ratio of 12% is used as a positive electrode, and sodium sheets and potassium sheets are used as negative electrodes to assemble a battery, which comprises the following specific steps:
compared with the first embodiment, the high-temperature fluorination heat preservation temperature in the step (4) is reduced from 500 ℃ to 450 ℃, and other experimental conditions are the same as the first embodiment;
the maximum discharge current density of the sodium/graphite fluoride micro-sheet battery prepared in the embodiment can reach 3500 milliamp/gram, the discharge specific capacity is 429.53 milliamp/gram, the maximum discharge current density of the potassium/graphite fluoride micro-sheet battery can reach 2000 milliamp/gram, and the discharge specific capacity is 401.25 milliamp/gram.
Example eight
In this embodiment, the prepared graphite fluoride micro-sheet with a fluorocarbon ratio of 0.82 and a surface c=c bond ratio of 9% is used as a positive electrode, and sodium sheets and potassium sheets are used as negative electrodes to assemble a battery, which comprises the following specific steps:
compared with the first embodiment, the high-temperature fluorination heat preservation time in the step (4) is reduced from 6 hours to 3 hours, and other experimental conditions are the same as the first embodiment;
the maximum discharge current density of the sodium/graphite fluoride micro-sheet battery prepared in the embodiment can reach 3100 milliamp/gram, the discharge specific capacity is 399.74 milliamp/gram, the maximum discharge current density of the potassium/graphite fluoride micro-sheet battery can reach 2200 milliamp/gram, and the discharge specific capacity is 344.26 milliamp/gram.
Comparative example one
In the comparative example, a prepared graphite fluoride micron sheet with a fluorocarbon ratio of 1.02 and a surface C=C bond ratio of less than 0.1% is taken as a positive electrode, and a sodium sheet and a potassium sheet are taken as a negative electrode to assemble a battery, and the battery is specifically as follows:
in the comparative example, compared with the first example, alloy balls and stirring paddles are not used in the steps (2), (3) and (4), and other experimental conditions are the same as the first example;
the maximum discharge current density of the sodium/graphite fluoride micro-sheet battery prepared in the comparative example can reach 1200 milliamp/gram, the discharge specific capacity is 724.22 milliamp/gram, the maximum discharge current density of the potassium/graphite fluoride micro-sheet battery can reach 700 milliamp/gram, and the discharge specific capacity is 682.33 milliamp/gram.
Comparative example two
In the comparative example, a prepared graphite fluoride micron sheet with a fluorocarbon ratio of 1.01 and a surface C=C bond ratio of less than 0.1% is taken as a positive electrode, and a sodium sheet and a potassium sheet are taken as a negative electrode to assemble a battery, and the battery is specifically as follows:
in the comparative example, compared with the first example, only the alloy balls were added in the steps (2), (3) and (4), no stirring paddle was used, and other experimental conditions were the same as the first example;
the maximum discharge current density of the sodium/graphite fluoride micro-sheet battery prepared in the comparative example can reach 1200 milliamp/gram, the discharge specific capacity is 719.64 milliamp/gram, the maximum discharge current density of the potassium/graphite fluoride micro-sheet battery can reach 700 milliamp/gram, and the discharge specific capacity is 661.16 milliamp/gram.
Comparative example three
In the comparative example, a prepared graphite fluoride micron sheet with a fluorocarbon ratio of 1.03 and a surface C=C bond ratio of less than 0.1% is taken as a positive electrode, and a sodium sheet and a potassium sheet are taken as a negative electrode to assemble a battery, and the battery is specifically as follows:
compared with the first embodiment, the comparative example does not add alloy balls in the steps (2), (3) and (4), only uses stirring paddles, and other experimental conditions are the same as the first embodiment;
the maximum discharge current density of the sodium/graphite fluoride micro-sheet battery prepared in the comparative example can reach 1200 milliamp/gram, the discharge specific capacity is 722.41 milliamp/gram, the maximum discharge current density of the potassium/graphite fluoride micro-sheet battery can reach 800 milliamp/gram, and the discharge specific capacity is 707.62 milliamp/gram.
Comparative example four
In the comparative example, a prepared graphite fluoride micron sheet with a fluorocarbon ratio of 1.06 and a surface C=C bond ratio of 4% is taken as a positive electrode, and sodium sheets and potassium sheets are taken as negative electrodes to assemble a battery, and the battery is specifically as follows:
in the comparative example, compared with the first example, in the step (2), the mass ratio of the alloy ball to the graphite is adjusted from 20:1 to 50:1, and other experimental conditions are the same as the first example;
the maximum discharge current density of the sodium/graphite fluoride micro-sheet battery prepared in the comparative example can reach 1800 milliamp/gram, the discharge specific capacity is 689.11 milliamp/gram, the maximum discharge current density of the potassium/graphite fluoride micro-sheet battery can reach 1000 milliamp/gram, and the discharge specific capacity is 691.20 milliamp/gram.
Please refer to tables 1-3, which illustrate the positive electrode materials and battery performance for all examples of the present invention versus comparative examples, from which it can be seen that:
1) In the embodiment 1, when the mass ratio of the alloy balls to the graphite micron sheets is 20:1, the rotation speed of the stirring paddle is 300 r/min, and the fluorination is carried out for 6 hours at 500 ℃, the graphite fluoride micron sheets with high fluorine-carbon ratio and highest surface C=C bond ratio can be obtained, and the graphite fluoride micron sheets are taken as sodium-potassium primary batteries of positive electrode active substances, the multiplying power performance and the specific capacity are also best, wherein the maximum discharge current density of the sodium/graphite fluoride micron sheet batteries can reach 4000 milliampere/g, the discharge specific capacity is 448.13 milliampere hour/g, the maximum discharge current density of the potassium/graphite fluoride micron sheet batteries can reach 3000 milliampere/g, and the discharge specific capacity is 428.44 milliampere hour/g;
2) In example 1, the sodium and potassium primary batteries all show excellent high and low temperature performance, and as shown in fig. 4 and 5, the batteries can normally operate in a wide temperature range of-30 to 100 ℃, and the potential application is wide; in addition, after a long storage period of 120 days, the attenuation of the working voltage platform and the discharge specific capacity of the battery is less than 5% compared with the first electrochemical performance, which shows that the battery has small self-discharge, low self-loss and excellent storage performance, and is shown in fig. 6 and 7;
3) Graphite fluoride obtained by a conventional fluorination method in the comparative example is used as a positive electrode active material of a sodium and potassium primary battery, wherein the maximum discharge rate of the sodium primary battery is 1200 milliamperes/gram, the maximum discharge rate of the potassium primary battery is 700 milliamperes/gram, and the battery rate performance is inferior to that of the battery in the example, so that the important influence of the C=C bond content on the surface of the graphite fluoride microchip on the battery rate performance can be shown.
TABLE 1
TABLE 2
TABLE 3 Table 3
In summary, the embodiment of the invention provides a preparation method of a high-rate primary alkali metal battery, which comprises the steps of shearing, emulsifying and homogenizing worm graphite to obtain graphite micro-sheets, carrying out high-temperature fluorination with the assistance of alloy balls to obtain graphite fluoride micro-sheets, dissolving the graphite fluoride micro-sheets serving as active substances, a conductive agent and a binder in proportion, pulping, coating on a current collector, drying and cutting to obtain a battery anode; wherein, the proportion of C=C bonds on the surface of the graphite fluoride micron sheet is 5-15%; removing a surface passivation layer from the metal sodium block or the metal potassium block, dropwise adding a plurality of electrolyte, and calendaring and cutting the metal sodium block or the metal potassium block into metal sodium sheets or metal potassium sheets with a first size through mechanical action to serve as a battery cathode; assembling a battery anode, a battery cathode, a diaphragm and electrolyte to obtain a sodium/graphite fluoride micron-sized primary battery or a potassium/graphite fluoride micron-sized primary battery; the battery has excellent discharge rate performance, wide working temperature range, good storage performance, excellent comprehensive performance and large application potential.
The foregoing description is only of the preferred embodiments of the present invention, and is not intended to limit the scope of the present invention. Any modification, equivalent replacement, improvement, etc. made within the spirit and scope of the present invention are included in the protection scope of the present invention.
Claims (6)
1. A method for preparing a high-rate primary alkali metal cell, the method comprising:
shearing, emulsifying and homogenizing worm graphite to obtain graphite micro-sheets, carrying out high-temperature fluorination with the aid of alloy balls to obtain graphite fluoride micro-sheets, dissolving the graphite fluoride micro-sheets serving as active substances, a conductive agent and a binder in proportion, pulping, coating the active substances on a current collector, drying and cutting to obtain a battery anode; wherein, the C=C bond on the surface of the graphite fluoride micron sheet is 5-15%;
the alloy balls are obtained by processing Monel alloy, the diameters of the alloy balls are 5, 10 and 15 millimeters respectively, the number ratio of the corresponding alloy balls is 4:2:1, and the mass ratio of the alloy balls to the graphite micron sheets is 10-30:1;
wherein, during high temperature fluorination, the temperature is raised to 180 ℃ at a temperature raising speed of 2 ℃ per minute, the temperature is kept for 1 to 3 hours, then the temperature is raised to 400 to 500 ℃ at a temperature raising speed of 4 ℃ per minute, the temperature is kept for 3 to 6 hours, and the temperature lowering speed is controlled to 4 to 6 ℃ per minute until the room temperature is reached;
removing the surface passivation layer from the metal sodium block or the metal potassium block, then dripping electrolyte, and calendaring and cutting the metal sodium block or the metal potassium block into metal sodium sheets or metal potassium sheets with a first size through mechanical action to serve as a battery cathode;
and assembling the battery anode, the battery cathode, the diaphragm and the electrolyte to obtain the sodium/graphite fluoride micron-sized sheet primary battery or the potassium/graphite fluoride micron-sized sheet primary battery.
2. The method for manufacturing a high-rate primary alkali metal cell according to claim 1, further comprising:
(1) Mixing worm graphite with the granularity of 10-100 micrometers in deionized water according to the proportion of 10-20%, shearing and emulsifying the mixed solution at a high speed of 2000-4000 rpm for 30-90 minutes, then maintaining the homogeneous solution for 30-60 minutes under the pressure of 1000-1500 pascals by a high-pressure homogenizer, and carrying out suction filtration and vacuum drying to obtain graphite micro-sheets;
(2) Adding the graphite micron sheets and alloy balls with different sizes and proportions into a fluorination furnace with stirring paddles, sealing, vacuumizing, removing oxygen and moisture in a bin by using inert gas at 100 ℃, and repeating for 3 times;
(3) Turning on a stirring paddle at the rotating speed of 100-500 rpm, turning over the alloy balls and the graphite micro-sheets, switching fluorine/nitrogen mixed gas with the gas of 20%, controlling the pressure to be 80-90 kilopascals, and running for 30 minutes;
(4) Controlling the temperature in the furnace, firstly heating to 180 ℃ at a heating rate of 2 ℃ per minute, preserving heat for 1-3 hours, then heating to 400-500 ℃ at a heating rate of 4 ℃ per minute, preserving heat for 3-6 hours, controlling the cooling rate to 4-6 ℃ per minute until the temperature reaches the room temperature, vacuumizing, treating residual fluorine gas and byproducts in the extracted furnace by alkali liquor, and sieving the materials in the furnace by a 5-mesh screen to obtain the graphite fluoride micro-sheet.
3. The method for preparing a high-rate primary alkali metal battery according to claim 1, wherein the graphite fluoride micro-sheet has a fluorocarbon ratio of 0.8-1.1 and an electrical conductivity of 1 x 10 -8 To 9X 10 -8 The Siemens/meter range, the size distribution is 2-30 microns.
4. The preparation method of the high-rate primary alkali metal battery according to claim 1, wherein in the battery positive electrode, the mass percentage of the graphite fluoride micron sheet is 80-94%, the mass percentage of the conductive agent is 3-15%, and the mass percentage of the binder is 3-10%.
5. The method for preparing a high-rate primary alkali metal battery according to claim 1, wherein in the positive electrode of the battery, the conductive agent is at least one of acetylene black, ketjen black, super-P and carbon nanotubes, the binder is polytetrafluoroethylene or polyvinylidene fluoride, the solvent is N-methylpyrrolidone, and the current collector is aluminum foil or carbon-coated aluminum foil.
6. The method for preparing the high-rate primary alkali metal battery according to claim 1, wherein in the battery cathode, the mass of the pre-added electrolyte is 1-3% of the mass of the metal block in the processing process of the sodium metal block and the potassium metal block.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011555032.XA CN112670528B (en) | 2020-12-23 | 2020-12-23 | Preparation method of high-rate primary alkali metal battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011555032.XA CN112670528B (en) | 2020-12-23 | 2020-12-23 | Preparation method of high-rate primary alkali metal battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112670528A CN112670528A (en) | 2021-04-16 |
| CN112670528B true CN112670528B (en) | 2023-07-25 |
Family
ID=75408575
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011555032.XA Active CN112670528B (en) | 2020-12-23 | 2020-12-23 | Preparation method of high-rate primary alkali metal battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112670528B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113299912A (en) * | 2021-05-20 | 2021-08-24 | 西北核技术研究所 | Carbon fluoride composite positive electrode active material for lithium-carbon fluoride battery, and preparation method and application thereof |
| CN114583128B (en) * | 2022-03-07 | 2023-09-19 | 湘潭大学 | Controllable preparation method of surface highly conductive carbon fluoride |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59228361A (en) * | 1983-06-09 | 1984-12-21 | Asahi Chem Ind Co Ltd | Battery using graphite fluoride as positive active material |
| CN101486454A (en) * | 2008-01-17 | 2009-07-22 | 杨先金 | Industrial novel method for synthesizing graphite fluoride |
| CN103700858A (en) * | 2014-01-07 | 2014-04-02 | 厦门大学 | Sodium-perfluorocarbon primary battery |
| CN107316988A (en) * | 2017-05-16 | 2017-11-03 | 中国航发北京航空材料研究院 | It is a kind of for composite positive pole of lithium fluorocarbon battery and preparation method thereof |
| CN109817978A (en) * | 2019-01-16 | 2019-05-28 | 山东重山光电材料股份有限公司 | A kind of preparation method of high specific energy fluorinated graphene lithium battery |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2747177B1 (en) * | 2012-12-21 | 2017-07-12 | Karlsruher Institut für Technologie | Lithium/graphite fluoride primary battery and method for its manufacturing |
-
2020
- 2020-12-23 CN CN202011555032.XA patent/CN112670528B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59228361A (en) * | 1983-06-09 | 1984-12-21 | Asahi Chem Ind Co Ltd | Battery using graphite fluoride as positive active material |
| CN101486454A (en) * | 2008-01-17 | 2009-07-22 | 杨先金 | Industrial novel method for synthesizing graphite fluoride |
| CN103700858A (en) * | 2014-01-07 | 2014-04-02 | 厦门大学 | Sodium-perfluorocarbon primary battery |
| CN107316988A (en) * | 2017-05-16 | 2017-11-03 | 中国航发北京航空材料研究院 | It is a kind of for composite positive pole of lithium fluorocarbon battery and preparation method thereof |
| CN109817978A (en) * | 2019-01-16 | 2019-05-28 | 山东重山光电材料股份有限公司 | A kind of preparation method of high specific energy fluorinated graphene lithium battery |
Non-Patent Citations (1)
| Title |
|---|
| 《Improving the Energy Density and Power Density of CFx by Mechanical Milling: A Primary Lithium Battery Electrode》;M. Anji Reddy, et al.;ACS Appl. Mater. Interfaces;第第5卷卷;第11207页第1栏第1段至第11210页第2栏第1段 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112670528A (en) | 2021-04-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109256555B (en) | Chalcogenide composite positive electrode material, all-solid-state lithium battery and preparation methods thereof | |
| CN112670528B (en) | Preparation method of high-rate primary alkali metal battery | |
| JPH05190209A (en) | Liquid electrolyte and rechargeable chemical cell with lithium/carbon anode | |
| US6428929B1 (en) | Negative electrode for high-energy lithium-ion batteries and method of production | |
| CN113178548A (en) | Pre-sodium graphene negative pole piece, preparation method thereof and sodium ion battery | |
| CN114464873B (en) | Non-negative electrode ether high-voltage sodium secondary battery and preparation method thereof | |
| CN113644244B (en) | Chromium oxide/carbon fluoride/highly conductive substance composite material for lithium primary battery | |
| CN112661146B (en) | Preparation method of laminated fluorinated graphene for positive electrode of lithium battery | |
| CN115084562A (en) | Carbon fluoride based metal lithium battery and manufacturing method thereof | |
| CN115579453A (en) | Carbon-coated aluminum foil and preparation process thereof | |
| CN115548253A (en) | Self-supporting silicon-carbon composite film cathode and preparation method thereof | |
| CN110875471B (en) | Metal lithium @ carbon composite material, lithium metal anode, and preparation and application of lithium metal anode | |
| CN112382763A (en) | Organic matter/silicon composite material, battery cathode obtained from organic matter/silicon composite material and preparation method of battery cathode | |
| CN112687856B (en) | Preparation method of high-power lithium battery | |
| CN112687873B (en) | Preparation method of high-specific-energy lithium battery | |
| CN113206290B (en) | Method for modifying in-situ interface layer of solid electrolyte | |
| CN116812913B (en) | High-reversible-capacity hard carbon negative electrode material and preparation method thereof | |
| CN113285066B (en) | Vanadium phosphate @ carbon/expanded microcrystalline graphite composite negative electrode active material for potassium ion battery and preparation and application thereof | |
| US20210028437A1 (en) | Method of making an electrode with protection layers | |
| CN113471428A (en) | Method for improving graphite or graphene negative electrode stability of potassium ion battery and potassium ion battery | |
| CN115863652A (en) | Modified lithium ion battery anode slurry and preparation method and application thereof | |
| CN117832512A (en) | Modified current collector of negative-electrode-free sodium battery, and preparation method and application thereof | |
| CN116031410A (en) | Composite positive plate, preparation method and application | |
| JP2024046512A (en) | Electrode manufacturing method | |
| CN117410453A (en) | Lithium powder negative electrode, preparation method thereof and lithium battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |