All you need here is importing StringType and using lit and cast:
from pyspark.sql.types import StringType
from pyspark.sql.functions import lit
new_df = old_df.withColumn('new_column', lit(None).cast(StringType()))
A full example:
df = sc.parallelize([row(1, "2"), row(2, "3")]).toDF()
df.printSchema()
# root
# |-- foo: long (nullable = true)
# |-- bar: string (nullable = true)
new_df = df.withColumn('new_column', lit(None).cast(StringType()))
new_df.printSchema()
# root
# |-- foo: long (nullable = true)
# |-- bar: string (nullable = true)
# |-- new_column: string (nullable = true)
new_df.show()
# +---+---+----------+
# |foo|bar|new_column|
# +---+---+----------+
# | 1| 2| null|
# | 2| 3| null|
# +---+---+----------+
A Scala equivalent can be found here: Create new Dataframe with empty/null field values