CN104282934B - Novel high-energy density dynamic battery - Google Patents
Novel high-energy density dynamic battery Download PDFInfo
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Abstract
The present invention relates to lithium ion power battery technology field, and in particular to a kind of novel high-energy density dynamic battery.Including positive pole, barrier film, negative pole and electrolyte, negative pole includes negative current collector and negative active core-shell material, and negative active core-shell material is C Sn Si high power capacity composites, and positive electrode active materials are nickelic high power capacity ternary material LinNixAyBzO2, wherein：1.0≤n≤1.1,0.6≤x≤0.85,0≤y≤0.2,0≤z≤0.2, and x+y+z=1.The battery energy density of the novel high-energy density dynamic battery of the present invention improves more than 16%, and makes battery charge cutoff voltage bring up to 4.3V, and the normal temperature high voltage cycle performance of battery improves 25% or so in addition.
Description
Technical field
The present invention relates to lithium ion power battery technology field, and in particular to a kind of novel high-energy density dynamic battery.
Background technology
Lithium-ion-power cell has voltage high with respect to other batteries, and energy density is big, and good cycle, self discharge are little,
The advantages of memory-less effect, operating temperature range width.The structure of general lithium-ion-power cell is：With laminar, by positive pole
The battery core that piece, barrier film, negative plate are alternate and are formed（Or battery core is made with coiling form）, then connect outside terminal, be put into
Duricrust（Such as plastic housing, box hat, aluminum hull）Or in aluminum plastic film, inject electrolyte.Conventional lithium ion electrokinetic cell, positive pole are typically adopted
With materials such as nickle cobalt lithium manganate, LiFePO4, LiMn2O4, cobalt acid lithiums, negative pole is using traditional graphite type material, such as artificial stone
Ink, native graphite, hard carbon or soft carbon etc.；Electrolyte solvent typically adopts ethylene carbonate, propene carbonate, methyl ethyl carbonate
The materials such as ester, diethyl carbonate, discharge and recharge blanking voltage scope are 2.7-4.2V, exactly because current lithium-ion-power cell
Energy density be restricted, have impact on lithium-ion-power cell discharge and recharge blanking voltage, limit lithium-ion-power cell
Application.
Content of the invention
The invention aims to overcoming current lithium-ion-power cell not obtain preferably due to energy density
Lifted, so as to cause discharge and recharge blanking voltage break through in relatively low scope, significantly limit answering for lithium-ion-power cell
A kind of problem, there is provided novel high-energy density dynamic battery.Technical scheme is by the material using high power capacity
Expect the both positive and negative polarity as battery, improve the energy density of battery, the charge cutoff voltage and normal temperature so as to improve battery is high
Pressure cycle performance.
In order to reach foregoing invention purpose, the present invention is employed the following technical solutions：
A kind of novel high-energy density dynamic battery, including positive pole, barrier film, negative pole and electrolyte, negative pole includes negative pole collection
Fluid and negative active core-shell material, negative active core-shell material are C-Sn-Si high power capacity composites.
Lithium-ion-power cell uses graphite material as negative pole at present.The theoretical capacity of generally graphite material is
372mAh/g, commercially produced product peak capacity≤365mAh/g, this is just limited to a certain extent using graphite cathode institute
The energy density of the battery of making, and then limit the performance of battery.And C-Sn-Si high power capacity composite has higher appearance
Amount, its theoretical capacity can actually reach 400-800 mAh/g at present in 2000 mAh/g or so.Therefore can using this material
To effectively improve the energy density of battery, and then improve the performance of battery.
Preferably, the C-Sn-Si high power capacity composite is Si-SnC2O4, energy density >=500mAh/g.
The energy density of C-Sn-Si is higher, but cycle performance is but poor than graphite material.Si- prepared by the present invention
SnC2O4Material, can be effectively improved the cycle performance of C-Sn-Si materials.
Preferably, the Si-SnC2O4 is prepared from by following steps：
（1）The silica flour that a certain amount of particle diameter is 0.1-5 μm is taken, by Si-SnC2O4Middle Si and SnC2O4Mass ratio be 1-10:1
The desired amount of soluble tin salt is calculated and takes, silica flour is soluble in water with soluble tin salt, stir, obtain suspension,
Will be soluble in water for Soluble oxalate salt, obtain Soluble oxalate salting liquid；
（2）Mol ratio by soluble tin salt and Soluble oxalate salt is 1:1-1.3, Soluble oxalate salting liquid is fallen
Entering in suspension and being stirred continuously 1-3h, obtain reactant liquor, the pH that whole reaction system is adjusted with acid solution is 0.5-3.
（3）Reactant liquor is carried out separation of solid and liquid, the solid for obtaining through washing and temperature be 80-100 DEG C at dry after,
Obtain final product Si-SnC2O4.
Preferably, the soluble tin salt is stannous chloride or stannous sulfate, the Soluble oxalate salt is oxalic acid
Potassium, sodium oxalate or ammonium oxalate.
Preferably, positive pole includes plus plate current-collecting body and positive electrode active materials, positive electrode active materials are nickelic high power capacity three
First material.One of business-like obstacle of electric automobile is that course continuation mileage is shorter.By the positive pole and negative pole of high-energy-density of arranging in pairs or groups,
The energy density of made battery is improved to greatest extent can, so as to the course continuation mileage of prolongation electric automobile by a relatively large margin.
Preferably, the nickelic high power capacity ternary material is LinNixAyBzO2, wherein：1.0≤n≤1.1,0.6≤x
≤ 0.85,0≤y≤0.2,0≤z≤0.2, and x+y+z=1.
The high capacity density lithium-ion-power cell of existing market, typically adopts LinNi0.5Co0.2Mn0.3O2, wherein：
1.0≤n≤1.1,0.6≤x≤0.85 of the present invention, by the positive electrode using nickelic high power capacity, further may be improved
The energy density of battery.
The formula of nickelic ternary material is LinNixAyBzO2.Business-like electrokinetic cell
LinNixAyBzO2Material, general x≤0.5.In order to improve discharge performance, presently mainly realized by two aspects, first,
Reduce grain diameter, and particle diameter is generally 200-400nm, grain diameter is less, and the electric conductivity of material is better, and high rate performance is got over
Good, but the reduction with grain diameter, and the security performance of battery reduces, and is susceptible to the phenomenons such as acupuncture is on fire；Second, improve
Addition, but with the increase of nickelic ternary material content in material, although the energy of raising material that can be by a relatively large margin
Density, but cause micron order material structure unstable in cyclic process, easily there is deoxidation phenomenon, affect cycle performance of battery,
Even if positive pole film forming improvement can be carried out by electrolysis additive, but it is big fundamentally to solve nickelic micron order material
The problem of current cycle difference.And the present invention reaches the energy density of increase material by improving x, electric conductivity and forthright again is improve
Can, and particle diameter is between 1-2 μm, it is to avoid the adverse effect that little particle particle diameter brings, while it also avoid nickelic ternary material
The excessive adverse effect to battery that brings of material addition.
Nickelic ternary material used in this programme, primary particle particle diameter are 1-2 μm, and the ternary material of routine is 200-
400 nanometers.By controlling the content of Li metals in material, reduce the pH value of material, improve the processing characteristics of material；By preparing
Bulky grain material, optimizes microcosmic layer structure, increases the stability of material structure, improves material high current cycle performance.
Preferably, the A and B is respectively the one kind in metallic element Co, Mn and Al.
The preparation method of the nickelic high power capacity ternary material is：
(1) hydroxide precursor is produced：By soluble nickel salt together with two kinds in three kinds of cobalt salt, manganese salt or aluminium salt,
Precipitation reaction is carried out with the sodium hydroxide solution for being mixed with ammoniacal liquor, structural formula is formed for NixAyBz(OH)2Granular precursor, its
In：X+y+z=1,0.6≤x≤0.85,0≤y≤0.2,0≤z≤0.2, A and B are respectively in metallic element Co, Mn and Al
A kind of；Then scrubbed, dry, obtain hydroxide precursor；In the reaction, the concentration of ammoniacal liquor is controlled in 0.4-0.6mol/
L, NaOH control are controlled in 7.6-8.0 in 4-6mol/L, terminal pH value, and the primary particle size controlling of precursor is in 1-2 μ
m；
(2) by the hydroxide precursor for obtaining and lithium salts with mol ratio as Li/ (Ni+A+B)=1.1-1.3, mixed
Close, be allowed to be well mixed；
(3) high-temperature process：High-temperature process will be carried out under the mixture nitrogen protection of upper step gained；The sintering of high-temperature process
Temperature is 1000-1200 DEG C, and adopts ladder mode of heating, and at 900-1100 DEG C, the later stage sinters the control of initial stage sintering temperature
Temperature control is at 1100-1200 DEG C；Then cool down, crush, sieves the nickelic ternary anode material for lithium-ion batteries that obtain.
Preferably, the electrolyte includes 3-5 kind functional additives, and every kind of functional additive accounts for the quality of electrolyte
Percentage is W%, 1.0≤W≤5.0；The total amount of all functional additives account for electrolyte mass percent be N%, 5.0≤N≤
15.
The addition of functional additive is very few, does not have the due circulation for improving battery, high-temperature behavior；Addition mistake
Many, the cost of electrolyte can increase, while the electrical conductivity of electrolyte can be reduced, affect the high rate during charging-discharging of battery.
Preferably, the functional additive is selected from vinylene carbonate（VC）, propylene sulfite, fluoro ethylene carbonate
Ester（FEC）, vinylethylene carbonate（VEC）With catechol carbonic ester（CC）In any 3-5 kinds.
Compared with prior art, beneficial effect is the present invention：1）Positive pole uses nickelic high power capacity ternary material by battery energy
Metric density improves 16% or so；2）Negative pole makes battery energy density improve 14% left using C-Sn-Si high power capacity composites
Right；3）By coordinating the compound high-voltage functions electrolyte of functional additive, battery charge cutoff voltage is made to have brought up to 4.3V,
And the normal temperature high voltage cycle performance of battery improves 25% or so.
Specific embodiment
Explanation is further described to technical scheme below by specific embodiment.
If without specified otherwise, the raw material employed in embodiments of the invention is raw material commonly used in the art, implements
Method employed in example, is the conventional method of this area.
Si-SnC2O4Preparation：
（1）The silica flour that a certain amount of particle diameter is 0.1-5 μm is taken, by Si-SnC2O4Middle Si and SnC2O4Mass ratio be 1-10:1
The desired amount of soluble tin salt is calculated and takes, by silica flour and soluble tin salt（Stannous chloride or stannous sulfate）It is dissolved in water
In, stir, obtain suspension, by Soluble oxalate salt（Potassium oxalate, sodium oxalate or ammonium oxalate）Soluble in water, obtain soluble grass
Acid salt solution；
（2）Mol ratio by soluble tin salt and Soluble oxalate salt is 1:1-1.3, Soluble oxalate salting liquid is fallen
The pH for entering in suspension and adjusting whole reaction system is 0.5-3, is stirred continuously 1-3h, obtains reactant liquor；
（3）Reactant liquor is carried out separation of solid and liquid, the solid for obtaining through washing and temperature be 80-100 DEG C at dry after,
Obtain final product Si-SnC2O4.
The preparation of nickelic high power capacity ternary material：
(1) hydroxide precursor is produced：By soluble nickel salt together with two kinds in three kinds of cobalt salt, manganese salt or aluminium salt,
Precipitation reaction is carried out with the sodium hydroxide solution for being mixed with ammoniacal liquor, structural formula is formed for NixAyBz(OH)2Granular precursor, its
In：X+y+z=1,0.6≤x≤0.85,0≤y≤0.2,0≤z≤0.2, A and B are respectively in metallic element Co, Mn and Al
A kind of；Then scrubbed, dry, obtain hydroxide precursor；In the reaction, the concentration of ammoniacal liquor is controlled in 0.4-0.6mol/
L, NaOH control are controlled in 7.6-8.0 in 4-6mol/L, terminal pH value, and the primary particle size controlling of precursor is in 1-2 μ
m；
(2) by the hydroxide precursor for obtaining and lithium salts with mol ratio as Li/ (Ni+A+B)=1.1-1.3, mixed
Close, be allowed to be well mixed；
(3) high-temperature process：High-temperature process will be carried out under the mixture nitrogen protection of upper step gained；The sintering of high-temperature process
Temperature is 1000-1200 DEG C, and adopts ladder mode of heating, and at 900-1100 DEG C, the later stage sinters the control of initial stage sintering temperature
Temperature control is at 1100-1200 DEG C；Then cool down, crush, sieves the nickelic ternary anode material for lithium-ion batteries that obtain.
The Si-SnC prepared by said method2O4In for following embodiment.
Comparative example 1
Prepare anode pole piece：Nickle cobalt lithium manganate according to 92 weight portions（Ni5Co2Mn3O2), the conductive black of 2 weight portions
SP, the CNT of 2 weight portions（CNT）, the Kynoar of 4 weight portions（PVDF）, the N-N- dimethyl pyrazoles of 80 weight portions
The proportioning of pyrrolidone stirs to form slurries, is uniformly coated on positive pole base flow body rolling aluminum foil, is carried out with roller after drying
Roll, make anode pole piece.
Prepare cathode pole piece：Mix the Delanium of 95 weight portions, the conductive black SP of 1 weight portion, the carboxylic of 1.5 weight portions
The butadiene-styrene rubber (SBR) of sodium carboxymethylcellulose pyce (CMC) and 2.5 weight portions, and add the deionized water stirring shape of 140 weight portions
Into slurries, uniformly it is coated on negative pole base flow body electrolytic copper foil, is rolled with roller after drying, make cathode pole piece.
Prepare barrier film：Barrier film adopts thickness for 25 microns of microporous compound film（PP-PE-PP）.
Prepare electrolyte：Electrolyte using 1.3mol/L lithium hexafluoro phosphate be dissolved into dimethyl carbonate, methyl ethyl carbonate,
In ethylene carbonate, the ORGANIC SOLVENT MIXTURES of propylene carbonate ester, wherein dimethyl carbonate, methyl ethyl carbonate, ethylene carbonate,
The volume ratio of propylene carbonate ester is（40:40:10:10）.
Prepare shell：Shell adopts aluminum plastic film, aluminum plastic film to adopt thickness, for 152 microns, there is nylon layer, tack coat, PP
Layer, tack coat, aluminium foil, tack coat, PP shape sandwich layer by layer.
Prepare external terminal：Positive terminal adopts 0.2 millimeters thick aluminium material lug, and negative terminal is using 0.2 millimeter of copper plating
Nickel lug.
Prepare battery：With laminar, anode pole piece, barrier film, the alternate lamination of cathode pole piece are formed battery core, unidirectional welding
Lug；Then aluminum plastic film heat-sealing is carried out, electrolyte, heat-sealing sealing is injected；Carry out successively shelving-preliminary filling-evacuation-chemical conversion-partial volume,
Make 30Ah lithium-ion-power cells.
Embodiment 1
Prepare anode pole piece：Mix the nickelic high power capacity ternary material of 92 weight portions（Li1.04Ni0.8Co0.15Al0.05O2）, 2
The conductive black SP of weight portion, the CNT of 2 weight portions（CNT）, and the Kynoar of 4 weight portions（PVDF）, and add
Plus 80 the N-N- dimethyl pyrrolidones of weight portion stir to form slurries, be uniformly coated on positive pole base flow body rolling aluminum foil,
Rolled with roller after drying, made anode pole piece.
Prepare cathode pole piece：Mix the C-Sn-Si high power capacity composites of 90 weight portions（Si-SnC2O4）, 2 weight portions
Conductive black SP and the Kynoar of 8 weight portions（PVDF）, and add the N-N- dimethyl pyrrolidones of 140 weight portions and stir
Mix to form slurries, be uniformly coated on negative pole base flow body electrolytic copper foil, rolled with roller after drying, make negative pole pole
Piece.
Prepare barrier film：Barrier film adopts thickness for 25 microns of microporous compound film（PP-PE-PP）.
Prepare electrolyte：Electrolyte using 1.3mol/L lithium hexafluoro phosphate be dissolved into dimethyl carbonate, methyl ethyl carbonate,
In ethylene carbonate, the ORGANIC SOLVENT MIXTURES of propylene carbonate ester, wherein dimethyl carbonate, methyl ethyl carbonate, ethylene carbonate,
The volume ratio of propylene carbonate ester is（40:40:10:10）；Add functional additive fluorinated ethylene carbonate（FEC）, ethylene carbonate
Ethyl（VEC）, catechol carbonic ester（CC）, each functional additive accounts for the mass percent of electrolyte and is respectively：5%、3%、
1.5%.
Prepare shell：Shell adopts aluminum plastic film, aluminum plastic film to adopt thickness, for 152 microns, there is nylon layer, tack coat, PP
Layer, tack coat, aluminium foil, tack coat, PP shape sandwich layer by layer.
Prepare external terminal：Positive terminal adopts 0.2 millimeters thick aluminium material lug, and negative terminal is using 0.2 millimeter of copper plating
Nickel lug.
Prepare battery：With laminar, anode pole piece, barrier film, the alternate lamination of cathode pole piece are formed battery core, unidirectional welding
Lug；Then aluminum plastic film heat-sealing is carried out, electrolyte, heat-sealing sealing is injected；Carry out successively shelving-preliminary filling-evacuation-chemical conversion-partial volume,
Make 30Ah lithium-ion-power cells.
Embodiment 2
Prepare anode pole piece：Mix the nickelic high power capacity ternary material of 92 weight portions（Li1.04Ni0.8Co0.15Al0.05O2）, 2
The conductive black SP of weight portion, the CNT of 2 weight portions（CNT）, and the Kynoar of 4 weight portions（PVDF）, and add
Plus 80 the N-N- dimethyl pyrrolidones of weight portion stir to form slurries, be uniformly coated on positive pole base flow body rolling aluminum foil,
Rolled with roller after drying, made anode pole piece.
Prepare cathode pole piece：Mix the C-Sn-Si high power capacity composites of 92 weight portions（Si-SnC2O4）, 2 weight portions
Conductive black SP and the polyacrylic acid of 6 weight portions, and add the deionized water of 130 weight portions and stir to form slurries, uniformly
It is coated on negative pole base flow body electrolytic copper foil, is rolled with roller after drying, make cathode pole piece.
Prepare barrier film：Barrier film adopts thickness for 25 microns of microporous compound film（PP-PE-PP）.
Prepare electrolyte：Electrolyte using 1.3mol/L lithium hexafluoro phosphate be dissolved into dimethyl carbonate, methyl ethyl carbonate,
In ethylene carbonate, the ORGANIC SOLVENT MIXTURES of propylene carbonate ester, wherein dimethyl carbonate, methyl ethyl carbonate, ethylene carbonate,
The volume ratio of propylene carbonate ester is（40:40:10:10）；Add functional additive：Fluorinated ethylene carbonate（FEC）, ethylene carbonate
Ethyl（VEC）, vinylene carbonate（VC）, each functional additive accounts for the mass percent of electrolyte and is respectively：5%、3%、
3.5%.
Prepare shell：Shell adopts aluminum plastic film, aluminum plastic film to adopt thickness, for 152 microns, there is nylon layer, tack coat, PP
Layer, tack coat, aluminium foil, tack coat, PP shape sandwich layer by layer.
Prepare external terminal：Positive terminal adopts 0.2 millimeters thick aluminium material lug, and negative terminal is using 0.2 millimeter of copper plating
Nickel lug.
Prepare battery：With laminar, anode pole piece, barrier film, the alternate lamination of cathode pole piece are formed battery core, unidirectional welding
Lug；Then aluminum plastic film heat-sealing is carried out, electrolyte, heat-sealing sealing is injected；Carry out successively shelving-preliminary filling-evacuation-chemical conversion-partial volume,
Make 30Ah lithium-ion-power cells.
Embodiment 3
Prepare anode pole piece：Mix the nickelic high power capacity ternary material of 92 weight portions（Li1.03Ni0.8Co0.1Mn0.1O2）, 2 weights
The conductive black SP of amount part, the CNT of 2 weight portions（CNT）, and the Kynoar of 4 weight portions（PVDF）, and add
The N-N- dimethyl pyrrolidones of 80 weight portions stir to form slurries, are uniformly coated on positive pole base flow body rolling aluminum foil, do
Rolled with roller after dry, made anode pole piece.
Prepare cathode pole piece：Mix the C-Sn-Si high power capacity composites of 92 weight portions（Si-SnC2O4）, 2 weight portions
Conductive black SP and the polyacrylic acid of 6 weight portions, and add the deionized water of 130 weight portions and stir to form slurries, uniformly
It is coated on negative pole base flow body electrolytic copper foil, is rolled with roller after drying, make cathode pole piece.
Prepare barrier film：Barrier film adopts thickness for 25 microns of microporous compound film（PP-PE-PP）.
Prepare electrolyte：Electrolyte using 1.3mol/L lithium hexafluoro phosphate be dissolved into dimethyl carbonate, methyl ethyl carbonate,
In ethylene carbonate, the ORGANIC SOLVENT MIXTURES of propylene carbonate ester, wherein dimethyl carbonate, methyl ethyl carbonate, ethylene carbonate,
The volume ratio of propylene carbonate ester is（40:40:10:10）；Add functional additive：Vinylene carbonate（VC）, sulfurous acid propylene
Ester, fluorinated ethylene carbonate（FEC）, vinylethylene carbonate（VEC）With catechol carbonic ester（CC）, each functional additive accounts for
The mass percent of electrolyte is respectively：3%、1%、3.5%、5%、2%.
Prepare shell：Shell adopts aluminum plastic film, aluminum plastic film to adopt thickness, for 152 microns, there is nylon layer, tack coat, PP
Layer, tack coat, aluminium foil, tack coat, PP shape sandwich layer by layer.
Prepare external terminal：Positive terminal adopts 0.2 millimeters thick aluminium material lug, and negative terminal is using 0.2 millimeter of copper plating
Nickel lug.
Prepare battery：With laminar, anode pole piece, barrier film, the alternate lamination of cathode pole piece are formed battery core, unidirectional welding
Lug；Then aluminum plastic film heat-sealing is carried out, electrolyte, heat-sealing sealing is injected；Carry out successively shelving-preliminary filling-evacuation-chemical conversion-partial volume,
Make 30Ah lithium-ion-power cells.
Performance comparison
1st, energy density test：
The various embodiments described above and battery obtained in comparative example 1 are respectively taken 3 measure, 25 DEG C of energy densities.Assay method is：
Then electric current is turned constant-voltage charge with 15A constant current charges to 4.3V at 25 DEG C, by electric current 3000mA；Shelve 10 points
Clock, is discharged to assigned voltage with 15A constant currents, determines the discharge capacity for obtaining battery；After shelving 10 minutes, repeat above-mentioned step
Rapid 3 times, calculate 3 discharge capacity mean values.Weight of the service precision for the dissimilar battery of electronic balance weighing of 0.1g.Press
25 DEG C of battery energy densities are calculated according to following formula：
Battery energy density=electric discharge average size × 3.6V/ battery weights.
Battery energy density test result is shown in Table 1.
As seen from the table, each embodiment battery energy density is 236-245Wh/Kg, and 1 battery energy density of comparative example is
180 Wh/Kg.Embodiment test result is far superior to comparative example 1, and this explanation is increased substantially using the battery that this invention makes
The energy density of battery.
2nd, 25 DEG C of -4.3V life performances tests：
Above-mentioned comparative example 1 and battery obtained in each embodiment are respectively taken 3, and it is remaining to determine the capacity after 500 circulations
Rate.Assay method is：Then electric current is turned constant-voltage charge, by electric current with 15A constant current charges to 4.3V at 25 DEG C
3000mA；Shelve 10 minutes, assigned voltage is discharged to 15A constant currents, determine the initial discharge capacity for obtaining battery；Shelve
After 10 minutes, repeat the above steps 500 times make continuous charge-discharge test, and the capacity obtained after 500 circulations of battery is remaining
Rate, calculates the capacity surplus ratio of battery after 500 circulations according to the following formula.
Discharge capacity/initial discharge capacity × 100% after the circulation of capacity surplus ratio=500 time.
Cycle life performance test result is shown in Table 1.As seen from the table, capacity surplus ratio of the embodiment after 500 circulations
In 83.3%-85.4%, and capacity attenuation of the comparative example 1 after 500 circulations is 80.2%.Embodiment test result is far superior to
Comparative example 1, this explanation improve the cycle of higher pressure life-span of battery using the battery that this invention makes.
1 battery performance contrast table of table
| Detection project | Battery energy density（Wh/Kg） | Capacity surplus ratio (%) after 25 DEG C of -500 circulations |
| Comparative example 1 | 180 | 80.2% |
| Embodiment 1 | 240 | 83.3% |
| Embodiment 2 | 245 | 84.7% |
| Embodiment 3 | 236 | 85.4% |
Above-described embodiment is only intended to description and interpretation present disclosure, it is impossible to constitute limitation of the scope of the invention.
Although inventor has done to the present invention and has enumerated in more detail, those skilled in the art is according to content of the invention portion
Divide and the content disclosed in embodiment, various modifications or/and supplement can be made to described specific embodiment or using similar
Mode be obvious to substitute.
Claims (7)
1. a kind of novel high-energy density dynamic battery, including positive pole, barrier film, negative pole and electrolyte, it is characterised in that negative pole bag
Negative current collector and negative active core-shell material is included, negative active core-shell material is C-Sn-Si high power capacity composites, the C-Sn-Si height
Capacity compound material is Si-SnC2O4, energy density >=500mAh/g, Si-SnC2O4It is prepared from by following steps：
（1）The silica flour that a certain amount of particle diameter is 0.1-5 μm is taken, by Si-SnC2O4Middle Si and SnC2O4Mass ratio be 1-10:1 calculates
And the desired amount of soluble tin salt is taken, and silica flour is soluble in water with soluble tin salt, stir, obtain suspension, can
Dissolubility oxalates is soluble in water, obtains Soluble oxalate salting liquid, and the soluble tin salt is stannous chloride or stannous sulfate, can
Dissolubility oxalates is potassium oxalate, sodium oxalate or ammonium oxalate；
（2）Mol ratio by soluble tin salt and Soluble oxalate salt is 1:1-1.3, Soluble oxalate salting liquid is poured into outstanding
In turbid liquid and 1-3h is stirred continuously, obtains reactant liquor；The pH for adjusting whole reaction system with acid solution is 0.5-3；
（3）Reactant liquor is carried out separation of solid and liquid, the solid for obtaining, is obtained final product after drying through washing and in the case where temperature is for 80-100 DEG C
Si-SnC2O4.
2. novel high-energy density dynamic battery according to claim 1, it is characterised in that positive pole includes plus plate current-collecting body
And positive electrode active materials, positive electrode active materials are nickelic high power capacity ternary material.
3. novel high-energy density dynamic battery according to claim 2, it is characterised in that the nickelic high power capacity ternary
Material is LinNixAyBzO2, wherein：1.0≤n≤1.1,0.6≤x≤0.85,0≤y≤0.2,0≤z≤0.2, and x+y+z=1.
4. novel high-energy density dynamic battery according to claim 3, it is characterised in that the A and B are respectively metal
One kind in Elements C o, Mn and Al.
5. novel high-energy density dynamic battery according to claim 4, it is characterised in that the nickelic high power capacity ternary
The preparation method of material is：
(1) hydroxide precursor is produced：By soluble nickel salt together with two kinds in three kinds of cobalt salt, manganese salt or aluminium salt, and mixed
The sodium hydroxide solution for having ammoniacal liquor carries out precipitation reaction, forms structural formula for NixAyBz(OH)2Granular precursor, wherein：x+y
+ z=1,0.6≤x≤0.85,0≤y≤0.2,0≤z≤0.2, A and B are respectively the one kind in metallic element Co, Mn and Al；So
By washing, dry, obtain hydroxide precursor；In the reaction, the concentration of ammoniacal liquor is controlled in 0.4-0.6mol/L, hydroxide
Sodium control is controlled in 7.6-8.0 in 4-6mol/L, endpoint pH, and the primary particle size controlling of precursor is at 1-2 μm；
(2) by the hydroxide precursor for obtaining and lithium salts with mol ratio as Li/ (Ni+A+B)=1.1-1.3, mixed, made
Be well mixed；
(3) high-temperature process：High-temperature process will be carried out under the mixture nitrogen protection of upper step gained；The sintering temperature of high-temperature process
For 1000-1200 DEG C, and adopt ladder mode of heating, the control of initial stage sintering temperature at 900-1100 DEG C, later stage sintering temperature
Control is at 1100-1200 DEG C；Then cool down, crush, sieves the nickelic ternary anode material for lithium-ion batteries that obtain.
6. novel high-energy density dynamic battery according to claim 1, it is characterised in that the electrolyte includes 3-5
Kind of functional additive, and every kind of functional additive to account for the mass percent of electrolyte be W%, 1.0≤W≤5.0；Institute is functional to be added
Plus the total amount of agent account for electrolyte mass percent be N%, 5.0≤N≤15.
7. novel high-energy density dynamic battery according to claim 6, it is characterised in that the functional additive is selected from
Appointing in vinylene carbonate, propylene sulfite, fluorinated ethylene carbonate, vinylethylene carbonate and catechol carbonic ester
Meaning 3-5 kinds.
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| CN103746143A (en) * | 2013-12-10 | 2014-04-23 | 宁波维科电池股份有限公司 | High energy density lithium ion power battery |
| CN104733724A (en) * | 2015-03-31 | 2015-06-24 | 南通瑞翔新材料有限公司 | Positive electrode material for high-nickel lithium ionic secondary battery and preparation method thereof |
| CN108075178B (en) * | 2016-11-18 | 2023-04-07 | Sk新能源株式会社 | Lithium secondary battery and method for manufacturing same |
| US10756331B2 (en) | 2016-11-18 | 2020-08-25 | Sk Innovation Co., Ltd. | Lithium secondary battery and method of fabricating the same |
| CN113690424B (en) * | 2021-10-26 | 2022-01-07 | 天津师范大学 | Carbon-tin-silicon negative electrode material of lithium ion battery and preparation method thereof |
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