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Introduction of Key Technology of Cathode Materials --- Ternary Cathode

 I. Material systems and basic theory

1.1 Chemical composition and crystal structure of trivalent materials


The crystal structure of the ternary cathode materials (lini _ xCo _ yMn _ zO _ 2 or lini _ xCo _ yAl _ zO _ 2) is a lamellar a-NaFeO _ 2 type, with space group R-3m. Nickel cobalt manganese (aluminum) ions occupy the 3a position, lithium ions occupy the 3b position, and oxygen ions occupy the 6c position. Nickel content directly affects:


Specific capacity : Ni²+ / Ni⁴+ redox couple provides the main capacity ( about 15-20mAh / g per 10% increase in Ni content )


Structural stability : High Ni material ( Ni ≥ 80 % ) is prone to H2 → H3 phase transition , resulting in lattice distortion rate of more than 6 %


Thermal stability : Thermal decomposition temperature decreases by about 15 ℃ per 10 % increase in nickel content



1.2 Technology comparison of low- and medium-nickel and high-nickel systems


System type

Typical Model

Nickel content

Specific capacity (mAh / g)

Heat out of control temperature

Medium and Low Nickel

NCM523

50-70%

155-175

220-250℃

NCM622

165-185

High Nickel

NCM811

≥80%

195-220

180-210℃

NCA90

200-220


II. Deep analysis of precursor preparation processes

2.1 Cohesion reaction mechanism

Reactions that occur in a continuously stirred reactor (CSTR):

Ni²+ + Co²+ + Mn²+ + 2OH⁻ → (NiCoMn)(OH)₂↓


Four phases of control:

Nucleation stage (0-30min): pHThe value jumps to more than 10.5, forming 5-20nm crystal nuclei


Growth stage ( 1-10h ) : Ostwald ripening dominates , D50 increases to 3-5μm


Densification stage ( 10-20h ) : surface energy is controlled by ammonia concentration , densification density is 1.8-2.2g / cm3


Curing stage ( 2-4h ) : Eliminate internal stress , reduce BET surface area to 10-15m2 / g


2.2 Critical equipment and parameter matrix


1 Level 5 serial reactor system (specialty for high nickel):

Bus Station

Temperature control

PH range

Ammonia concentration (g / L)

Mixing power (kW / m3)

1#

55±0.5℃

11.8-12.2

2.0-2.5

3.5-4.0

2#

58±0.3℃

11.5-11.8

1.8-2.2

4.0-4.5

3#

60±0.2℃

11.2-11.5

1.5-1.8

4.5-5.0

4#

62±0.2℃

10.8-11.2

1.0-1.5

5.0-5.5

5#

65±0.1℃

10.5-10.8

0.5-1.0

5.5-6.0


2 Parameters of medium and low nickel materials:

Single reactor reaction time : 8-12h


Particle distribution: D10=2.5μm, D50=4.5μm, D90=8.0μm


Specific surface area : 12-18m2 / g


III. Core technologies of lithium blending and sintering processes


3.1 Lithium source selection and rationing calculation


The formula for the lithium overload coefficient:

Li / (Ni + Co + Mn) = 1.05-1.10 (low and medium nickel)

Li/(Ni+Co+Al) = 1.08-1.15(高镍)


Mixed manufacturing process comparison:

parameter

Dry method of mixing

Wet mixing

equipment

V-mixer

High Speed Hybrid

Planetary ball milling machine

speed

15-25rpm

200-500rpm

200-300rpm

time

2-4h

0.5-1h

4-6h

homogeneity

RSD≥5%

RSD≥5%

RSD≤2%

System of application

Medium and Low Nickel

System-wide

High Nickel



3.2 Sintering Dynamics and Equipment Selection


Push Plate Kiln vs Roller Kiln vs Return Kiln:

Indicator

Crane kiln (low and medium nickel)

Crane kilns (whole system)

Reverse kiln (high nickel)

Temperature uniformity

±5℃

±1℃

±1℃

Climate control

air

Air or oxygen

O2 concentration 5-15%

Rate of heating

3-5 °C/min

3-5 °C/min

1-2 °C/min

production capacity

200kg / batch

300kg / batch

500kg / day

Lithium residual control

1.2-1.8%

1.0-2.0%

0.8-1.2%



Typical sintering curves:

NCM622 : Room temperature → 400 ℃ (2h) → 750 ℃ (12h) → furnace cooling


NCM811: Room temperature → 300 ℃ (2h, O2 5%) → 500 ℃ (3h, O210%) → 750 ℃ (10h, O215%) → rapid cooling


IV. Post-treatment and surface modification techniques


4.1 Crushing grading process


Parameters for jet stream crushing machines:

Working pressure : 0.8-1.2MPa


Speed of classification wheel : 4000-8000rpm


D50 control accuracy : ± 0.3 μm


Production capacity : 100-300kg/h



Rating criteria:

Indicator

Low and medium nickel requirements

High nickel requirements

D10

2. 0-3.0μm

3. 0-4.0μm

D50

4. 0-5.0μm

5. 0-6.5μm

D90

10μm

12μm

Length coefficient

<1.2

<1.0


4.2 Surface cladding techniques


Wet cladding process:

Coating agent : AlPO₄ , Li₂TiO₃ , LiAlO₂


Reaction conditions : solid-liquid ratio 1 : 3 , 80 ℃ , pH = 9-10 , stirring for 2 h


Coating thickness : 2-5nm


Coating amount : 0.5-2.0wt %


Atomic layer deposition (ALD) technology:

Deposited material : Al₂O₃ , TiO₂


Deposition rate : 0.1nm / cycle


Vacuum of equipment: 10⁻³ Pa


Film uniformity : > 95 %


V. Key performance indicators and test methods


5.1 Electrochemical properties

Test projects

Methodological standards

Typical values of medium and low nickel

High nickel target value

First efficiency

GB/T 30835

85-88%

88-92%

1C cycle life

25℃,2.8-4.3V

1500 weeks ≥ 80%

1000 weeks ≥ 90%

High temperature performance

Storage at 45 ° C for 7 days

Capacity maintained at ≥ 95%

≥92%

DCIR elongation

1C cycle 500 weeks

<25%

<15%


5.2 Physical properties

parameter

Test equipment

Control standards

Vibration density

Hall Flow Rate Meter

≥2.2g/cm³

Compared to surface area

BET nitrogen sorbent

0.3-0.8m²/g

Magnetic foreign objects

High-gradient magnetic sorting machine

≤100ppb

Water content

Calffaut Water Meter

≤500ppm


VI. Core influencing factors and control strategies


6.1 Quality control of raw materials

Elements of impurities

Allowable upper limit (ppm)

Effect mechanisms

Na

<50

Blocking the diffusion of lithium ions

Ca

<20

Generating a LiCaPO4 Blocking Channel

Fe

<10

Catalyst for Electrolyte Decomposition

S

<100

Formation of Li2SO4 increases interface impedance


6.2 Tolerance analysis of process parameters

working procedure

Key parameters

Allowable range of volatility

Impact on performance

Together, we settled

PH value

±0.05

★★★★★

Ammonia Concentration

±0.1g/L

★★★★☆

Sinter

Maximum temperature

±3℃

★★★★★

Oxygen Concentration

±1vol%

★★★★☆

smash

Level wheel speed

±50rpm

★★★☆☆


VII. Frontier technologies and development trends


7.1 Breakthroughs in monocrystalline technology

Synthesis process : Melt salt method ( LiNO₃-LiOH co-melting system )


Single crystal size : 3-5μm


Improved cycle performance : 1C / 2000 cycles > 88 % capacity retention


7.2 Concentration gradient materials

Composition of nuclear layer : Ni80Co10Mn10


Shell composition : Ni50Co20Mn30


Thickness of transition layer : 200-500nm


Improved thermal stability : DSC peak temperature increased by 30 ℃


7.3 Solid-state battery adaptation technology

Interface modification : LiNbO₃ / LiTaO₃ coating


Sintering temperature optimization : 850-950 ℃


Ion conductivity: > 10⁻⁴ S/cm (Matching with sulfide electrolytes)


VIII. CONCLUSIONS

The industrial production of trivalent cathode materials has formed a complete technical system from raw material refinement (metal purity ≥ 99.95%), precursor synthesis (particle size CV value < 10%), to sintering process (oxygen pressure closed-loop control).

For high-nickel materials, it is necessary to establish a process-wide inert gas protection system (dew point ≤ -40 ° C, oxygen content ≤ 10 ppm), and to introduce online laser particle analysis (sampling every 30 seconds) and real-time XRD monitoring (fluctuation of lattice parameters a and c values ≤ 0.005Å per batch detection).

With the maturity of technologies such as multi-element mixing (Mg / Ti / Zr co-mixing) and microstructure regulation (secondary spherical porosity 15-20%), triad materials are continuously evolving towards higher energy density (≥ 300 Wh / kg) and longer cycle life (≥ 1500 weeks).


——End——

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