CN107785584A - A kind of sodium-ion battery anode additive NaCrO2/ C and its preparation method and application - Google Patents

A kind of sodium-ion battery anode additive NaCrO2/ C and its preparation method and application Download PDF

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CN107785584A
CN107785584A CN201710897650.4A CN201710897650A CN107785584A CN 107785584 A CN107785584 A CN 107785584A CN 201710897650 A CN201710897650 A CN 201710897650A CN 107785584 A CN107785584 A CN 107785584A
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sodium
nacro
additive
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徐茂文
沈博磊
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Southwest University
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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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

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Abstract

The present invention relates to a kind of sodium-ion battery anode additive NaCrO2/ C and its preparation method and application, belong to sodium-ion battery technical field, the anode additive has height ratio capacity, a small amount of addition is only needed to provide for enough sodium ions during use, and the additive does not interfere with the performance of positive electrode, because the additive is transformed into the CrO of no electro-chemical activity when sodium ion is all deviate from from the anode additive2So that sodium ion in charge and discharge process not further into additive lattice, meanwhile, the additive will not also be influenceed in full battery discharge by overdischarge.Experiment shows, by adding NaCrO2/ C can make full battery efficiency lift more than one times.The method for preparing the anode additive is simple and cost is cheap, is adapted to produce in enormous quantities, it is most important that need not carry out upgrading being used in the production of sodium-ion battery to current lithium ion battery production equipment, have very big commercial significance.

Description

A kind of sodium-ion battery anode additive NaCrO2/ C and its preparation method and application
Technical field
The invention belongs to sodium-ion battery technical field, and in particular to a kind of sodium-ion battery anode additive NaCrO2/C And its preparation method and application.
Background technology
Current era, due to the popularization of electric car, and the unstability of the new energy such as wind energy, solar energy, tide energy, people It is also more and more urgent to the demand of large-scale electric storage device.Yet with the scarcity of lithium resource, cause lithium ion battery large-scale Development on electric storage device is very limited.Under this serious situation, developing low-cost and the almost limitless sodium ion of resource Battery has outstanding meaning.
But sodium-ion battery industrialization still faces heavy predicament, though the nowadays research of sodium-ion battery positive material is Substantially tend to be ripe, also there is that hundreds and thousands of kinds of negative materials are available, but after positive pole and negative pole are assembled, assembled The full battery gone out all suffers from the problem of efficiency is extremely low.This phenomenon mainly has two reasons, and one is due to sodium ion ratio Lithium ion is easier to be present in negative material in the form of solid solution, is difficult to once sodium ion forms solid solution sodium from negative pole Deintercalation comes out again in the lattice of material；Two be due to that the SEI films of sodium-ion battery and the SEI film components of lithium ion battery differ Sample, the main component of lithium ion battery SEI films is LiF, and the main component of sodium-ion battery SEI films is Na2CO3, it means that The sodium ion that sodium-ion battery is consumed when generating SEI films is more than lithium ion.In order to solve this problem, most of research people Negative pole can be carried out pre- sodium by member before full battery is assembled, but the pre- sodium modification method of negative pole reported at present can all use gold Belong to sodium, and metallic sodium is expensive, and chemical property is very active, in wet condition can spontaneous combustion, meeting water, then vigorous reaction is even Blast, can undoubtedly greatly improve production cost and risk, this is also current sodium-ion battery in actual production using metallic sodium Bottleneck problem in full battery industry.Therefore, the commercialization to sodium-ion battery that solves the above problems has great meaning.
The content of the invention
In view of this, the present invention is solved the above problems by adding rich sodium material in positive electrode, utilizes rich sodium material Material can provide extra sodium ion in formation process and negative pole is passivated, and the full battery efficiency of sodium ion is improved so as to reach Effect, therefore, it is an object of the invention to：(1) a kind of sodium-ion battery anode additive NaCrO is provided2/ C preparation method； (2) a kind of sodium-ion battery anode additive NaCrO is provided2/C；(3) a kind of sodium-ion battery anode additive NaCrO is provided2/ Applications of the C in sodium-ion battery.
To reach above-mentioned purpose, the present invention provides following technical scheme：
1st, a kind of sodium-ion battery anode additive NaCrO2/ C preparation method, comprises the following steps：
(1) NaCrO is prepared2Presoma：By sodium element and the mol ratio 1 of chromium:1~1.5:1 is equal by sodium source and chromium source Ball milling 5~24 hours after even mixing, NaCrO is made2Presoma；
(2) NaCrO is prepared2Pure phase：By obtained NaCrO in step (1)2Presoma is at 900~1100 DEG C in indifferent gas Calcined 5~24 hours in atmosphere, NaCrO is made2Pure phase；
(3) low temperature bag carbon：By NaCrO2With the mass ratio 1 of carbon source:0.2~1:5 NaCrO that will be prepared in step (2)2It is pure Ball milling 5~24 hours, is then calcined 8~24 hours at 500~600 DEG C in inert atmosphere after mutually uniformly being mixed with carbon source, Sodium-ion battery anode additive NaCrO is made2/C。
Further, in step (1), the mol ratio 1.1 of the sodium element and chromium:1.
Further, in step (1), the time of the ball milling is 12 hours.
Further, in step (1), the sodium source is sodium carbonate, sodium acid carbonate, sodium dihydrogen phosphate, disodium hydrogen phosphate or hydrogen One or more in sodium oxide molybdena, it is preferred that the sodium source is sodium carbonate.
Further, in step (1), the chromium source is in chrome green, nine water chromic nitrates, chromium trichloride or chromium sulfate It is one or more, it is preferred that the chromium source is chrome green.
Further, in step (2), the calcining is to be calcined 5 hours in inert atmosphere at 900 DEG C.
Further, in step (3), the carbon source is sucrose, fructose, chitosan, starch, dopamine, oleic acid, terephthaldehyde One or more in acid, 1,3,5-Benzenetricarboxylic acid or Pyromellitic Acid, it is preferred that the carbon source is sucrose.
Further, in step (3), the NaCrO2Mass ratio with carbon source is 1:1.
Further, in step (3), the time of the ball milling is 12 hours.
Further, in step (3), the calcining is to be calcined 12 hours in inert atmosphere at 600 DEG C.
Further, in step (2) and step (3), the inert atmosphere is the gaseous mixture of argon gas, nitrogen, hydrogen and argon gas Or the one or more in the gaseous mixture of hydrogen and nitrogen, it is preferred that the inert atmosphere is argon gas.
2nd, sodium-ion battery anode additive NaCrO prepared by described preparation method2/C。
3rd, described NaCrO2Applications of/the C in sodium-ion battery.
Further, the preparation method of the sodium-ion battery is as follows：
A, positive plate is prepared：By positive electrode, NaCrO2/ C, conductive agent and binding agent, which are added in solvent, is made black after grinding The thick slurry I of color, the slurry I is applied on collector, and after drying process, positive plate is made；
B, negative plate is prepared：Hard carbon, conductive agent and binding agent are added in solvent after grinding and the slurry of dark thick shape is made Material II, the slurry II is applied on collector, and after drying process, negative plate is made；
C, full battery is assembled：The step A positive plates prepared and step the B negative plate prepared are subjected to battery assembling, obtained Full battery.
Further, in step A, the positive electrode, NaCrO2/ C, conductive agent and binding agent mass ratio are 5:3:1:1； The positive electrode is Na3V2O2(PO4)2F/RGO, the conductive agent be acetylene black, conductive carbon black or Ketjen black in one kind or A variety of, the binding agent is Kynoar, and the solvent is 1-Methyl-2-Pyrrolidone, and the collector is aluminium foil.
Further, in step B, the mass ratio of the hard carbon, conductive agent and binding agent is 8:1:1；The conductive agent is second One or more in acetylene black, conductive carbon black or Ketjen black；The bonding agent is Kynoar, carboxymethyl cellulose or polyphenyl One or more in ethylene butadiene copolymers, the solvent be 1-Methyl-2-Pyrrolidone or deionized water one kind or A variety of, the collector is one kind in aluminium foil or copper foil.
The beneficial effects of the present invention are：The invention provides a kind of sodium-ion battery anode additive NaCrO2/ C and its Preparation method and application, the anode additive have a height ratio capacity, only need during use a small amount of addition provide for enough sodium from Son, and the additive does not interfere with the performance of positive electrode, because when sodium ion is all deviate from from the anode additive The additive is transformed into the CrO of no electro-chemical activity2So that sodium ion is in charge and discharge process not further into additive In lattice, meanwhile, the additive will not also be influenceed in full battery discharge by overdischarge.Experiment shows, passes through addition NaCrO2/ C can make full battery efficiency lift more than one times.The method for preparing the anode additive is simple and cost is cheap, is adapted to Produce in enormous quantities, it is most important that upgrading can need not be carried out to current lithium ion battery production equipment and is used in sodium ion In the production of battery, there is very big commercial significance.
Brief description of the drawings
In order that the purpose of the present invention, technical scheme and beneficial effect are clearer, the present invention provides drawings described below and carried out Explanation：
Fig. 1 is the NaCrO prepared in embodiment 12/ C XRD；
Fig. 2 is the NaCrO prepared in embodiment 12/ C charge-discharge performance figure；
Fig. 3 be embodiment 7 in additive-free pole piece half-cell and have additive pole piece half-cell charge-discharge performance figure and (a is the charge-discharge performance figure of additive-free pole piece half-cell to cycle performance figure, and b is the cyclicity of additive-free pole piece half-cell It can scheme, c is the charge-discharge performance figure for having additive pole piece half-cell, and d is the cycle performance figure for having additive pole piece half-cell)；
Fig. 4 is the full battery of additive-free pole piece and to have the charge-discharge performance figure (a of the full battery of additive pole piece in embodiment 8 For the full battery charging and discharging performance map of additive-free pole piece, b is to have the full battery charging and discharging performance map of additive pole piece).
Embodiment
The preferred embodiments of the present invention will be described in detail below.
Embodiment 1
Prepare sodium-ion battery anode additive NaCrO2/C
(1) NaCrO is prepared2Presoma：By sodium element and the mol ratio 1.1 of chromium:1 by sodium carbonate and chrome green Uniformly ball milling 12 hours after mixing, are made NaCrO2Presoma；
(2) NaCrO is prepared2Pure phase：By obtained NaCrO in step (1)2Presoma is forged at 900 DEG C in argon gas atmosphere Burn 5 hours, NaCrO is made2Pure phase；
(3) low temperature bag carbon：By NaCrO2With the mass ratio 1 of sucrose:1 NaCrO that will be prepared in step (2)2Pure phase and sucrose Uniformly ball milling 12 hours after mixing, are then calcined 12 hours at 600 DEG C in argon gas atmosphere, and sodium-ion battery positive pole is made and adds Add agent NaCrO2/C。
Embodiment 2
Prepare sodium-ion battery anode additive NaCrO2/C
(1) NaCrO is prepared2Presoma：By sodium element and the mol ratio 1.2 of chromium:1 by disodium hydrogen phosphate and nine water nitre Ball milling 8 hours after sour chromium uniformly mixes, is made NaCrO2Presoma；
(2) NaCrO is prepared2Pure phase：By obtained NaCrO in step (1)2Presoma is at 1000 DEG C in hydrogen and argon gas Calcined 15 hours in mixed atmosphere, NaCrO is made2Pure phase；
(3) low temperature bag carbon：By NaCrO2With the mass ratio 1 of chitosan:1.5 NaCrO that will be prepared in step (2)2Pure phase and Ball milling 8 hours, is then calcined 20 hours at 550 DEG C in hydrogen and argon gas mixed atmosphere after chitosan uniformly mixes, and is made Sodium-ion battery anode additive NaCrO2/C。
Embodiment 3
Prepare sodium-ion battery anode additive NaCrO2/C
(1) NaCrO is prepared2Presoma：By sodium element and the mol ratio 1.3 of chromium:1 by sodium hydroxide and chromium trichloride Uniformly ball milling 5 hours after mixing, are made NaCrO2Presoma；
(2) NaCrO is prepared2Pure phase：By obtained NaCrO in step (1)2Presoma mixes at 900 DEG C in hydrogen and nitrogen Close and calcined 24 hours in atmosphere, NaCrO is made2Pure phase；
(3) low temperature bag carbon：By NaCrO2With the mass ratio 1 of dopamine:2.5 NaCrO that will be prepared in step (2)2Pure phase and Ball milling 5 hours, is then calcined 16 hours at 600 DEG C in hydrogen and nitrogen mixture atmosphere after dopamine uniformly mixes, and is made Sodium-ion battery anode additive NaCrO2/C。
Embodiment 4
Prepare sodium-ion battery anode additive NaCrO2/C
(1) NaCrO is prepared2Presoma：By sodium element and the mol ratio 1.4 of chromium:1 is equal by sodium acid carbonate and chromium sulfate Ball milling 24 hours after even mixing, NaCrO is made2Presoma；
(2) NaCrO is prepared2Pure phase：By obtained NaCrO in step (1)2Presoma is at 1100 DEG C in nitrogen atmosphere Calcining 10 hours, NaCrO is made2Pure phase；
(3) low temperature bag carbon：By NaCrO2With the mass ratio 1 of 1,3,5-Benzenetricarboxylic acid:5 NaCrO that will be prepared in step (2)2Pure phase Ball milling 24 hours after uniformly being mixed with 1,3,5-Benzenetricarboxylic acid, then calcined 8 hours in nitrogen atmosphere at 500 DEG C, be made sodium from Sub- anode additive NaCrO2/C。
Embodiment 5
Prepare sodium-ion battery anode additive NaCrO2/C
(1) NaCrO is prepared2Presoma：By sodium element and the mol ratio 1.5 of chromium:1 aoxidizes sodium dihydrogen phosphate and three Ball milling 16 hours after two chromium uniformly mix, is made NaCrO2Presoma；
(2) NaCrO is prepared2Pure phase：By obtained NaCrO in step (1)2Presoma is at 1000 DEG C in argon gas atmosphere Calcining 20 hours, NaCrO is made2Pure phase；
(3) low temperature bag carbon：By NaCrO2With the mass ratio 1 of starch:0.2 NaCrO that will be prepared in step (2)2Pure phase and shallow lake Ball milling 16 hours, is then calcined 24 hours at 550 DEG C in argon gas atmosphere after powder uniformly mixes, and sodium-ion battery positive pole is made Additive NaCrO2/C。
Embodiment 6
To the anode additive NaCrO prepared in embodiment 12/ C carries out X-ray diffraction, as a result as shown in figure 1, by Fig. 1 Understand, the anode additive NaCrO synthesized by method in embodiment 12/ C peak intensities are obvious, and very identical with PDF cards, Illustrate that this method can successfully synthesize the very high NaCrO of purity2。
In mass ratio 8:1:1 by NaCrO in embodiment 12/ C, acetylene black and Kynoar add 1- methyl -2- pyrroles In alkanone, the slurry of dark thick shape is made after grinding, the slurry is applied on aluminium foil, after drying process, be made NaCrO2/ C electrode slices；By metallic sodium, barrier film and above-mentioned prepared NaCrO2/ C electrode slices carry out the assembling of button cell, institute The button cell model used is CR2032, and barrier film model whatman GF/D, electrolyte is 1mol/L NaClO4Solution (solvent is ethylene carbonate and dimethyl carbonate by volume 1:The mixed liquor of 1 composition), after assembling, by battery removal hand Casing, tested after standing 6h at 30 DEG C in Land test systems, test result is as shown in Fig. 2 as shown in Figure 2, positive pole Additive NaCrO2After/C specific capacity is 200mAh/g, and sodium ion is released in first lap charging, the second circle discharge capacity is almost It is zero, is because NaCrO2/ C is changed into the CrO of no electro-chemical activity after whole sodium ions are discharged2, the material can not be again Embedded sodium ion, will not be influenceed by full battery over-discharge.
Embodiment 7
NaCrO2The influence tests of/C to positive electrode
1st, the making of additive-free positive plate
In mass ratio 8:1:1 by positive electrode Na3V2O2(PO4)2F/RGO, acetylene black and polyvinylidene fluoride add 1- methyl -2- In pyrrolidones, the slurry of dark thick shape is made after grinding, the slurry is applied on aluminium foil, after drying process, be made Additive-free positive plate；
2nd, there is the making of additive positive plate
In mass ratio 5:3:1:1 by positive electrode Na3V2O2(PO4)2F/RGO, anode additive NaCrO2/ C, acetylene black and Kynoar adds in 1-Methyl-2-Pyrrolidone the slurry that dark thick shape is made after grinding, and the slurry is applied to On aluminium foil, after drying process, the positive plate for having additive is made；
3rd, additive-free pole piece half-cell performance and there is additive pole piece half-cell performance test
With reference to battery assembly method in embodiment 6, respectively using above-mentioned additive-free positive plate and have additive positive plate as Raw material makes assembling and obtains additive-free pole piece half-cell and have additive pole piece half-cell, and after assembling, half-cell is moved Go out glove box, tested respectively in Land test systems after standing 6h at 30 DEG C, test result is as shown in figure 3, wherein, scheme A is the charge-discharge performance figure of additive-free pole piece half-cell in 3, and b is the cyclical stability of additive-free pole piece half-cell in Fig. 3 Figure, c is the charge-discharge performance figure for having additive pole piece half-cell in Fig. 3, and d is the circulation for having additive pole piece half-cell in Fig. 3 Stability diagram, a and c is understood in comparison diagram 3, with the addition of NaCrO2After/C, the sodium ions content that positive plate is released in charging is bright Aobvious increase, illustrates NaCrO2/ C can provide extra sodium ion in charging process really, and the curve basic one when discharging Cause, illustrate NaCrO2/ C loses activity after sodium ion is discharged, and influences very little to positive pole.B and d is understood in comparison diagram 3, is added NaCrO2After/C, positive plate cycle performance is barely affected under same multiplying power, further illustrates NaCrO2To electricity after/C inactivations Pond influences very little.
Embodiment 8
NaCrO2Liftings of/the C to full battery performance
1st, the making of negative plate
In mass ratio 8:1:1 adds hard carbon, acetylene black and Kynoar in 1-Methyl-2-Pyrrolidone, after grinding The slurry of dark thick shape is made, the slurry is applied on aluminium foil, after drying process, negative plate is made.
2nd, the assembling and performance test of additive-free full battery
With reference to battery assembly method in embodiment 6, by the additive-free positive plate prepared in embodiment 7 and above-mentioned negative plate The assembling of button cell is carried out, after assembling, is stood by battery removal glove box, at 30 DEG C after 6h in Land test systems Tested, test result is as shown in a in Fig. 4.
3rd, there are the assembling and performance test of the full battery of additive
With reference to battery assembly method in embodiment 6, there are additive positive plate and above-mentioned negative plate by what is prepared in embodiment 7 The assembling of button cell is carried out, after assembling, is stood by battery removal glove box, at 30 DEG C after 6h in Land test systems Tested, test result is as shown in b in Fig. 4.
A and b is understood in comparison diagram 4, and additive-free full battery discharge specific capacity only has 45mAh/g, and with the addition of positive pole and add The full battery discharge specific capacity for adding agent is 96mAh/g, lifts more than one times by contrast.
Finally illustrate, preferred embodiment above is merely illustrative of the technical solution of the present invention and unrestricted, although logical Cross above preferred embodiment the present invention is described in detail, it is to be understood by those skilled in the art that can be Various changes are made to it in form and in details, without departing from claims of the present invention limited range.

Claims (10)

  1. A kind of 1. sodium-ion battery anode additive NaCrO2/ C preparation method, it is characterised in that comprise the following steps：
    (1) NaCrO is prepared2Presoma：By sodium element and the mol ratio 1 of chromium:1~1.5:1 uniformly mixes sodium source and chromium source Ball milling 5~24 hours afterwards, NaCrO is made2Presoma；
    (2) NaCrO is prepared2Pure phase：By obtained NaCrO in step (1)2Presoma is at 900~1100 DEG C in inert atmosphere Calcining 5~24 hours, NaCrO is made2Pure phase；
    (3) low temperature bag carbon：By NaCrO2With the mass ratio 1 of carbon source:0.2~1:5 NaCrO that will be prepared in step (2)2Pure phase and Ball milling 5~24 hours, is then calcined 8~24 hours at 500~600 DEG C in inert atmosphere after carbon source uniformly mixes, and is made Sodium-ion battery anode additive NaCrO2/C。
  2. A kind of 2. sodium-ion battery anode additive NaCrO as claimed in claim 12/ C preparation method, it is characterised in that In step (1), the sodium source be sodium carbonate, sodium acid carbonate, sodium dihydrogen phosphate, disodium hydrogen phosphate or sodium hydroxide in one kind or It is a variety of.
  3. A kind of 3. sodium-ion battery anode additive NaCrO as claimed in claim 12/ C preparation method, it is characterised in that In step (1), the chromium source is the one or more in chrome green, nine water chromic nitrates, chromium trichloride or chromium sulfate.
  4. A kind of 4. sodium-ion battery anode additive NaCrO as claimed in claim 12/ C preparation method, it is characterised in that In step (3), the carbon source be sucrose, fructose, chitosan, starch, dopamine, oleic acid, terephthalic acid (TPA), 1,3,5-Benzenetricarboxylic acid or One or more in Pyromellitic Acid.
  5. A kind of 5. sodium-ion battery anode additive NaCrO according to any one of claims 1 to 42/ C preparation method, its It is characterised by, in step (2) and step (3), the inert atmosphere is the gaseous mixture or hydrogen of argon gas, nitrogen, hydrogen and argon gas With the one or more in the gaseous mixture of nitrogen.
  6. 6. the sodium-ion battery anode additive NaCrO prepared as the preparation method described in any one of Claims 1 to 52/C。
  7. 7. the NaCrO described in claim 62Applications of/the C in sodium-ion battery.
  8. 8. application as claimed in claim 7, it is characterised in that the preparation method of the sodium-ion battery is as follows：
    A, positive plate is prepared：By positive electrode, NaCrO2Black is made after grinding in/C, conductive agent and binding agent addition solvent to glue The slurry I of thick shape, the slurry I is applied on collector, after drying process, positive plate is made；
    B, negative plate is prepared：Hard carbon, conductive agent and binding agent are added in solvent after grinding and the slurry II of dark thick shape are made, The slurry II is applied on collector, after drying process, negative plate is made；
    C, full battery is assembled：The step A positive plates prepared and step the B negative plate prepared are subjected to battery assembling, obtain full electricity Pond.
  9. 9. application as claimed in claim 8, it is characterised in that in step A, the positive electrode, NaCrO2/ C, conductive agent and The mass ratio of binding agent is 5:3:1:1；The positive electrode is Na3V2O2(PO4)2F/RGO, the conductive agent are acetylene black, led Electrical carbon is black or Ketjen black in one or more, the binding agent is Kynoar, and the solvent is 1- methyl -2- pyrrolidines Ketone, the collector are aluminium foil.
  10. 10. application as claimed in claim 8, it is characterised in that in step B, the quality of the hard carbon, conductive agent and binding agent Than for 8:1:1；The conductive agent is the one or more in acetylene black, conductive carbon black or Ketjen black；The bonding agent is poly- inclined One or more in PVF, carboxymethyl cellulose or polystyrenebutadienes copolymer, the solvent are 1- methyl -2- pyrroles The one or more of pyrrolidone or deionized water, the collector are one kind in aluminium foil or copper foil.
CN201710897650.4A 2017-09-28 2017-09-28 A kind of sodium-ion battery anode additive NaCrO2/ C and its preparation method and application Pending CN107785584A (en)

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CN109052474A (en) * 2018-07-03 2018-12-21 中南大学 A kind of preparation method and application of bulky grain chromous acid sodium material
CN109786660A (en) * 2018-12-17 2019-05-21 中国电子科技集团公司第十八研究所 Sodium ion battery electrode capable of carrying out positive electrode pre-sodium treatment
CN111293290A (en) * 2018-12-10 2020-06-16 中南大学 Sodium-rich transition metal oxide composite sodium-supplementing positive electrode active material, positive electrode, preparation method of positive electrode and application of positive electrode in sodium electrovoltaics
CN113093031A (en) * 2021-03-19 2021-07-09 北京工业大学 Method for detecting overdischarge degree of lithium ion battery anode material based on voltage reverse thrust
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CN113620345A (en) * 2021-10-12 2021-11-09 中国科学院过程工程研究所 Sodium chromite material and preparation method and application thereof
CN116119715A (en) * 2023-01-03 2023-05-16 中国科学院过程工程研究所 Sodium chromite material and preparation method and application thereof

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CN109052474A (en) * 2018-07-03 2018-12-21 中南大学 A kind of preparation method and application of bulky grain chromous acid sodium material
CN111293290A (en) * 2018-12-10 2020-06-16 中南大学 Sodium-rich transition metal oxide composite sodium-supplementing positive electrode active material, positive electrode, preparation method of positive electrode and application of positive electrode in sodium electrovoltaics
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CN113130896A (en) * 2019-12-30 2021-07-16 珠海冠宇电池股份有限公司 Positive electrode material for sodium ion battery and sodium ion battery comprising same
CN113093031A (en) * 2021-03-19 2021-07-09 北京工业大学 Method for detecting overdischarge degree of lithium ion battery anode material based on voltage reverse thrust
CN113620345A (en) * 2021-10-12 2021-11-09 中国科学院过程工程研究所 Sodium chromite material and preparation method and application thereof
CN113620345B (en) * 2021-10-12 2022-03-11 中国科学院过程工程研究所 Sodium chromite material and preparation method and application thereof
CN116119715A (en) * 2023-01-03 2023-05-16 中国科学院过程工程研究所 Sodium chromite material and preparation method and application thereof

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